Binder compositions and methods for making and using same

ABSTRACT

Binder compositions and methods for making and using same are provided. In at least one specific embodiment, the binder composition can include at least one unsaturated compound having two or more unsaturated carbon-carbon bonds and at least one free radical precursor. At least one of the unsaturated carbon-carbon bonds can be a pi-bond that is not conjugated with an aromatic moiety and can be capable of free radical addition. The free radical precursor can be present in an amount of about 7 wt % to about 99 wt %, based on the weight of the one or more unsaturated compounds.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of co-pending U.S. patent applicationSer. No. 15/810,127, filed on Nov. 12, 2017, which is a continuation ofU.S. patent application Ser. No. 15/056,112, filed on Feb. 29, 2016, nowU.S. Pat. No. 9,815,928, which is a continuation of U.S. patentapplication Ser. No. 14/948,467, filed on Nov. 23, 2015, now U.S. Pat.No. 9,273,223, which is a divisional of U.S. patent application Ser. No.14/205,440, filed on Mar. 12, 2014, now U.S. Pat. No. 9,193,894, whichclaims priority to U.S. Provisional Patent Application No. 61/782,265,filed on Mar. 14, 2013, which are all incorporated by reference herein.

BACKGROUND Field

Embodiments described herein generally relate to binder compositionsthat include one or more unsaturated prepolymers and methods for makingand using same. More particularly, embodiments described herein relateto binder compositions that include one or more unsaturated prepolymersfor making lignocellulose composite products.

Description of the Related Art

The production of lignocellulose composite products requires an adhesiveor binder to bond the discrete, particulates, fibers, veneers, or othersubstrates to one another. Typical lignocellulose composite productsinclude particleboard, fiberboard, plywood, oriented strand board (OSB),and the like. Conventional binders used in the production of theseproducts frequently contain formaldehyde based resins such asurea-formaldehyde (UF), melamine-formaldehyde (MF),melamine-urea-formaldehyde (MUF), and phenol-formaldehyde (PF) binders.While these formaldehyde based resins produce finished products havingdesirable properties, such as strength, these binders also releaseformaldehyde into the environment during the production of the binder,curing of the binder in the manufacture of a lignocellulose compositeproduct, as well as, from the final composite product made using thebinder.

Various techniques have been used to reduce the amount of formaldehydereleased from formaldehyde based resins. For example, the addition offormaldehyde scavengers to the resin and/or various modifications to theparticular synthesis steps used to make the formaldehyde based resin,such as the addition of urea as a reactant late in the binder synthesis,are often used in an attempt to reduce formaldehyde emission. Theseattempts to reduce formaldehyde emission, however, are accompanied withundesirable effects such as longer cure time, reduced resin shelf-life,reduced product strength, reduced tolerance for processing variations,and/or inferior moisture resistance.

There is a need, therefore, for improved binder compositions for makingcomposite lignocellulose containing products having reduced or noformaldehyde emission.

SUMMARY

Binder compositions and methods for making and using same are provided.In at least one specific embodiment, the binder composition can includeat least one unsaturated compound having two or more unsaturatedcarbon-carbon bonds and at least one free radical precursor. At leastone of the unsaturated carbon-carbon bonds can be a pi-bond (π-bond)that is not conjugated with an aromatic moiety and can be capable offree radical addition. The free radical precursor can be present in anamount of about 7 wt % to about 99 wt %, based on the weight of the oneor more unsaturated compounds.

In at least one specific embodiment, the method for making a compositeproduct can include combining a plurality of lignocellulose substrates,at least one unsaturated compound, and at least one free radicalprecursor to produce a mixture. The unsaturated compound can have two ormore unsaturated carbon-carbon bonds. At least one of the unsaturatedcarbon-carbon bonds can be a pi-bond that is not conjugated with anaromatic moiety and can be capable of free radical addition. The methodcan also include heating the mixture to a temperature of about 60° C. toabout 300° C. to produce a composite product.

In at least one specific embodiment, the composite product can include aplurality of lignocellulose substrates and an at least partially curedbinder composition. The binder composition, prior to at least partialcuring, can include at least one unsaturated compound and at least onefree radical precursor. The unsaturated compound can have two or moreunsaturated carbon-carbon bonds. At least one of the unsaturatedcarbon-carbon bonds can be a pi-bond that is not conjugated with anaromatic moiety and can be capable of free radical addition.

DETAILED DESCRIPTION

The one or more unsaturated compounds having two or more unsaturatedcarbon-carbon bonds and the one or more free-radical precursors can bemixed, blended, stirred, contacted, or otherwise combined with oneanother to produce the binder composition. The binder composition can becombined with a plurality of lignocellulose substrates to produce amixture. The mixture can also be referred to as a “furnish,” “blendedfurnish,” “resinated mixture,” or “resinated furnish.” As used herein,the terms “unsaturated compound” and “reactive unsaturated compound” areused interchangeably and refer to compounds having two or moreunsaturated carbon-carbon bonds, where at least one of the unsaturatedcarbon-carbon bonds is capable of free radical addition. As used herein,the phrase “capable of free radical addition,” when used in conjunctionwith “unsaturated compound” means that the carbon-carbon double bond isa pi-bond (π-bond) that is not conjugated with an aromatic moiety and iscapable of going through a free radical chain reaction mechanism. Thefree radical chain mechanism can include an initiation step, apropagation step, and a termination step. In one or more embodiments,the unsaturated carbon-carbon bond capable of free radical addition canbe of an alkene conjugated with a carbonyl group in an α,β-unsaturatedcarbonyl compound. The α,β-unsaturated carbonyl compound can include,but is not limited to, an aldehyde, a ketone, a carboxylic acid, anester, an amide, an acyl halide, an acid anhydride, or an imide. Forexample, the α,β-unsaturated carbonyl compound can be, but is notlimited to, an α,β-unsaturated aldehyde (e.g., an enal), anα,β-unsaturated ketone (e.g., an enone), an α,β-unsaturated carboxylicacid, an α,β-unsaturated ester, an α,β-unsaturated amide, anα,β-unsaturated acyl halide, an α,β-unsaturated acid anhydride, or anα,β-unsaturated imide. In one or more embodiments, the unsaturatedcompound can be substantially free or completely free from any aromaticmoiety.

The amount of the free radical precursor present in the bindercomposition can depend, at least in part, on the particular compositionof the free radical precursor, the particular composition of thelignocellulose substrates to which the binder composition can beapplied, and/or, the particular composition of the unsaturated compoundand, thus, can widely vary. For example, a weight ratio of the freeradical precursor to the unsaturated compound can be about 0.05:1, about0.1:1, about 0.2:1, about 0.3:1, a bout 0.4:1, about 0.5:1, about 0.6:1,about 0.7:1, about 0.8:1, about 0.9:1, or about 1:1 to about 3:1, about5:1, about 7:1, about 10:1, about 15:1, about 20:1, about 25:1, about30:1, about 35:1, or about 40:1. In another example, the weight ratio ofthe free radical precursor to the unsaturated compound can be about0.25:1 to about 0.65:1, about 0.35:1 to about 0.55:1, about 0.4:1 toabout 0.5:1, about 0.4:1 to about 0.45:1, about 0.45:1 to about 0.5:1,about 0.4:1 to about 1:1, about 1:1 to about 5:1, about 2:1 to about6:1, about 10:1 to about 33:1, about 17:1 to about 37:1, about 4:1 toabout 8:1, or about 0.1:1 to about 1:1. In another example, the weightratio of the free radical precursor to the unsaturated compound can beat least 0.1:1, at least 0.13:1, at least 0.15:1, at least 0.17:1, atleast 0.2:1, at least 0.23:1, at least 0.25:1, at least 0.27:1, at least0.3:1, at least 0.33:1, at least 0.35:1, at least 0.37:1, at least0.4:1, at least 0.43:1, at least 0.45:1, at least 0.47:1, at least0.5:1, at least 0.53:1, at least 0.55:1, at least 0.57:1, or at least0.6:1 to about 1:1, about 2:1, about 3:1, about 4:1, about 5:1, about10:1, about 20:1, about 30:1, or about 40:1. In yet another example, theweight ratio of the free radical precursor to the unsaturated compoundcan be about 0.15:1 to about 0.7:1, about 0.2:1 to about 8:1, about0.3:1 to about 0.6:1, about 0.3:1 to about 4:1, or about 0.4:1 to about2:1.

The weight ratio of the unsaturated compound to the free radicalprecursor in the binder composition can be about 0.02:1, about 0.025:1,about 0.05:1, about 0.1:1, about 0.3:1, about 0.5:1, about 0.7:1, orabout 1:1 to about 2:1, about 2.5:1, about 3:1, about 3.5:1, about 4:1,about 4.5:1, about 5:1, about 6:1, about 7:1, about 8:1, about 9:1, orabout 10:1. In another example, the weight ratio of the unsaturatedcompound to the free radical precursor can be about 0.025:1 to about10:1, about 0.1:1 to about 7.5:1, about 0.5:1 to about 5:1, about 0.3:1to about 2.5:1, about 0.5:1 to about 1.5:1, about 3:1 to about 7:1,about 4:1 to about 6:1, about 6:1 to about 10:1, or about 0.3:1 to about5.5:1. In another example, the weight ratio of the unsaturated compoundto the free radical precursor can be at least 0.02:1, at least 0.025:1,at least 0.3:1, at least 0.35:1, at least 0.4:1, at least 0.45:1, atleast 0.5:1, at least 0.6:1, at least 0.65:1, at least 0.7:1, at least0.75:1, at least 0.8:1, at least 0.85:1, at least 0.9:1, at least0.95:1, or at least 1:1 to about 3:1, about 4:1, about 5:1, about 6:1,about 7:1, about 8:1, about 9:1, or about 10:1. In yet another example,the weight ratio of the unsaturated compound to the free radicalprecursor can be about 0.125:1 to about 5:1, about 0.5:1 to about 3:1,about 1.5:1 to about 2.9:1, about 2:1 to about 4:1, or about 2.1:1 toabout 4.5:1.

In at least one specific embodiment, the amount of the free radicalprecursor in the binder composition can be about 1 wt %, about 3 wt %,about 5 wt %, about 7 wt %, about 9 wt %, about 10 wt %, about 12 wt %,about 15 wt %, about 20 wt %, about 25 wt %, about 30 wt %, about 35 wt%, or about 40 wt % to about 60 wt %, about 65 wt %, about 70 wt %,about 75 wt %, about 80 wt %, about 85 wt %, about 90 wt %, about 95 wt%, about 98 wt %, or about 99 wt %, based on the combined weight of theunsaturated compound and the free radical precursor. For example, theamount of the free radical precursor in the binder composition can beabout 7 wt % to about 99 wt %, about 7 wt % to about 98 wt %, about 10wt % to about 80 wt %, about 15 wt % to about 70 wt %, about 17 wt % toabout 66 wt %, about 10 wt % to about 45 wt %, about 35 wt % to about 75wt %, about 15 wt % to about 25 wt %, about 20 wt % to about 35 wt %,about 30 wt % to about 50 wt %, about 35 wt % to about 60 wt %, or about45 wt % to about 80 wt %, based on the combined weight of theunsaturated compound and the free radical precursor. In another example,the amount of the free radical precursor in the binder composition canbe at least 3 wt %, at least 5 wt %, at least 6 wt %, at least 7 wt %,at least 8 wt %, at least 9 wt %, at least 10 wt %, at least 15 wt %, atleast 20 wt %, at least 25 wt % at least 20 wt %, at least 35 wt %, atleast 40 wt %, or at least 45 wt % to about 50 wt %, about 55 wt %,about 60 wt %, about 65 wt %, about 70 wt %, about 75 wt %, about 80 wt%, about 85 wt %, about 90 wt %, or about 95 wt %, based on the combinedweight of the unsaturated compound and the free radical precursor. Inanother example, the amount of the free radical precursor in the bindercomposition can be less than 95 wt %, less than 90 wt %, less than 85 wt%, less than 80 wt %, less than 75 wt %, less than 70 wt %, less than 60wt %, less than 55 wt %, less than 50 wt %, less than 45 wt %, or less40 wt % and greater than 2 wt %, greater than 5 wt %, greater than 10 wt%, greater than 15 wt %, greater than 20 wt %, or greater than 25 wt %,based on the combined weight of the unsaturated compound and the freeradical precursor.

In at least one specific embodiment, the amount of the free radicalprecursor in the binder composition can be about 1 wt %, about 3 wt %,about 5 wt %, about 7 wt %, about 9 wt %, about 10 wt %, about 12 wt %,about 15 wt %, about 20 wt %, about 25 wt %, about 30 wt %, about 35 wt%, or about 40 wt % to about 60 wt %, about 65 wt %, about 70 wt %,about 75 wt %, about 80 wt %, about 85 wt %, about 90 wt %, about 95 wt%, or about 99 wt %, based on the weight of the unsaturated compound.For example, the amount of the free radical precursor in the bindercomposition can be about 7 wt % to about 99 wt %, about 10 wt % to about80 wt %, about 15 wt % to about 70 wt %, about 17 wt % to about 66 wt %,about 10 wt % to about 45 wt %, about 35 wt % to about 75 wt %, about 15wt % to about 25 wt %, about 20 wt % to about 35 wt %, about 30 wt % toabout 50 wt %, about 35 wt % to about 60 wt %, or about 45 wt % to about80 wt %, based on the weight of the unsaturated compound. In anotherexample, the amount of the free radical precursor in the bindercomposition can be present in an amount of at least 3 wt %, at least 5wt %, at least 6 wt %, at least 7 wt %, at least 8 wt %, at least 9 wt%, at least 10 wt %, at least 15 wt %, at least 20 wt %, at least 25 wt% at least 20 wt %, at least 35 wt %, at least 40 wt %, or at least 45wt % to about 50 wt %, about 55 wt %, about 60 wt %, about 65 wt %,about 70 wt %, about 75 wt %, about 80 wt %, about 85 wt %, about 90 wt%, or about 95 wt %, based on the weight of the unsaturated compound. Inanother example, the amount of the free radical precursor in the bindercomposition can be less than 95 wt %, less than 90 wt %, less than 85 wt%, less than 80 wt %, less than 75 wt %, less than 70 wt %, less than 60wt %, less than 55 wt %, less than 50 wt %, less than 45 wt %, or less40 wt % and greater than 2 wt %, greater than 5 wt %, greater than 6 wt%, greater than 7 wt %, greater than 8 wt %, greater than 9 wt %,greater than 10 wt %, greater than 15 wt %, greater than 20 wt %, orgreater than 25 wt %, based on the weight of the unsaturated compound.

In at least one specific embodiment, the amount of the unsaturatedcompound in the binder composition can be about 1 wt %, about 2 wt %,about 2.5 wt %, about 5 wt %, about 10 wt %, about 15 wt %, about 20 wt%, about 25 wt %, about 30 wt %, or about 35 wt % to about 60 wt %,about 65 wt %, about 70 wt %, about 75 wt %, about 80 wt %, about 85 wt%, about 90 wt %, about 93 wt %, or about 95 wt %, based on the combinedweight of the unsaturated compound and the free radical precursor. Forexample, the amount of the unsaturated compound in the bindercomposition can be about 10 wt % to about 85 wt %, about 30 wt % toabout 83 wt %, about 25 wt % to about 65 wt %, about 40 wt % to about 85wt %, about 35 wt % to about 75 wt %, about 20 wt % to about 40 wt %,about 30 wt % to about 50 wt %, about 40 wt % to about 60 wt %, about 50wt % to about 70 wt %, or about 70 wt % to about 90 wt %, based on thecombined weight of the unsaturated compound and the free radicalprecursor. In another example, the amount of the unsaturated compound inthe binder composition can be at least 3 wt %, at least 5 wt %, at least10 wt %, at least 15 wt %, at least 20 wt %, at least 25 wt % at least20 wt %, at least 35 wt %, at least 40 wt %, or at least 45 wt % toabout 50 wt %, about 55 wt %, about 60 wt %, about 65 wt %, about 70 wt%, about 75 wt %, about 80 wt %, about 85 wt %, about 90 wt %, or about95 wt %, based on the combined weight of the unsaturated compound andthe free radical precursor. In another example, the amount of theunsaturated compound in the binder composition can be less than 95 wt %,less than 90 wt %, less than 85 wt %, less than 80 wt %, less than 75 wt%, less than 70 wt %, less than 60 wt %, less than 55 wt %, less than 50wt %, less than 45 wt %, or less 40 wt % and greater than 2 wt %,greater than 5 wt %, greater than 10 wt %, greater than 15 wt %, greaterthan 20 wt %, or greater than 25 wt %, based on the combined weight ofthe unsaturated compound and the free radical precursor.

In one or more embodiments, the unsaturated compound can have a doublebond equivalent molecular weight of about 33, about 50, about 100, about150, about 200, about 500, about 1,000, about 5,000, about 10,000, orabout 15,000 to about 50,000, about 75,000, about 100,000, about150,000, about 200,000, or about 250,000. In one or more embodiments,the unsaturated compound can have a double bond equivalent molecularweight of at least 33, at least 40, at least 45, at least 50, at least75, at least 100, at least 200, at least 300, at least 400, at least500, at least 1,000, at least 2,500, at least 5,000, at least 10,000, atleast 20,000, at least 30,000, at least 40,000, at least 50,000, atleast 60,000, at least 70,000, at least 80,000, at least 90,000, atleast 100,000, at least 110,000, at least 120,000, at least 130,000, atleast 140,000, or at least 150,000 to about 175,000, about 200,000,about 225,000, or about 250,000.

As used herein, the double bond equivalent molecular weight can becalculated by dividing the molecular weight of the unsaturated compoundby the number of carbon-carbon double bonds the unsaturated compoundcontains. For example, if the unsaturated compound is cyclopentadiene,which has a molecular weight of 66.1 g/mol and two carbon-carbon doublebonds, the double bond equivalent molecular weight is 33.05 (66.1divided by 2). Accordingly, as used herein, the term “unsaturatedcompound” includes compounds that can be considered a monomer ordiscrete molecules. In another example, if the unsaturated compound istrimethylolpropane triacrylate (TMPTA), which has a molecular weight of296.32 g/mol and 3 carbon-carbon double bonds, the double bondequivalent molecular weight is 98.8.

In one or more embodiments, the unsaturated compound can have a weightaverage molecular weight (MW) of about 200, about 250, about 300, about350, about 400, about 450, about 500, about 550, about 600, or about 650to about 1,000, about 1,500, about 2,000, about 2,500, about 3,000,about 3,500, about 4,000, about 4,500, about 5,000, about 6,000, about7,000, about 8,000, about 9,000, or about 10,000. For example, theunsaturated compound can have a weight average molecular weight of about300 to about 3,000, about 330 to about 770, about 380 to about 930,about 470 to about 1,150, about 700 to about 1,800, about 800 to about2,200, about 1,200 to about 2,000, about 400 to about 2,800, about 500to about 2,700, about 600 to about 2,600, or about 700 to about 2,500.In one or more embodiments, the unsaturated compound can have a weightaverage molecular weight of at least 300, at least 325, at least 350, atleast 375, at least 400, at least 425, at least 450, at least 475, atleast 500, at least 525, at least 550, at least 575, at least 600, atleast 625, at least 650, at least 675, at least 700, at least 750, atleast 775, at least 800, at least 825, at least 850, at least 875, atleast 900, at least 925, at least 950, at least 975, or at least 1,000.

In one or more embodiments, the unsaturated compound can include, but isnot limited to, dicyclopentadiene (DCPD), 4-vinylcyclohexene, one ormore vinyl ethers, one or more allyl ethers, diallyl phthalate, allylcrotonate, allyl cinamate, allyl methacrylate, vinyl methacrylate,ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethyleneglycol diacrylate, diethylene glycol dimethacrylate, trimethylpropanetriacrylate, poly(ethylene glycol) diacrylate, poly(ethylene glycol)dimethacrylate, pentaerythritol tetraacrylate, pentaerythritoltriacrylate, polyacrylate, one or more conjugated dienes, one or moreterpenes, one or more drying oils having an iodine number of about 115or greater, one or more unsaturated prepolymers, one or more polyesterswith one or more incorporated vinyl unsaturations, styrene-butadienerubber (SBR), one or more starches having at least one unsaturated andpolymerizable olefinic group, polymers derived from ring-openingpolymerization of allyl caprolactone, a product or products formed byreacting one or more polyamidoamines and one or more unsaturatedglycidyl ethers, or any mixture thereof.

Illustrative vinyl aromatic compounds can include, but are not limitedto, 2-allylphenol, 4-allylphenol, and any mixture thereof. Illustrativevinyl ethers can include, but are not limited to, triethyleneglycoldivinyl ether, divinyl ether, or any mixture thereof. Illustrative allylethers can include, but are not limited to, diallyl ether,trimethylolpropane diallyl ether, triallyl cyanurate, or any mixturethereof. Illustrative conjugated dienes can include, but are not limitedto, 1,3-butadiene, 2,3-dimethylbutadiene, 2-methyl-1,3-butadiene(isoprene), 1,3-pentadiene (piperylene), cyclopentadiene,2-chloro-1,3-butadiene (chloroprene), or any mixture thereof. Anillustrative terpene can include, but is not limited to, one or moresesquiterpenes. An illustrative sesquiterpene can include, but is notlimited to, one or more farnesenes. Illustrative farnesenes includeα-Farnesene (3,7,11-trimethyl-1,3,6,10-dodecatetraene) and β-farnesene(7,11-dimethyl-3-methylene-1,6,10-dodecatriene) and the isomers thereof.Illustrative drying oils having an iodine number of about 115 or greatercan include, but are not limited to, linseed oil, soybean oil, sunfloweroil, tung oil, grape seed oil, wheat germ oil, corn oil, or any mixturethereof. In some examples, the drying oil can have an iodine number ofabout 115 to about 180, or greater. Illustrative unsaturated prepolymerscan include, but are not limited to, unsaturated polyester prepolymers,unsaturated polyether prepolymers, unsaturated polyamide prepolymers,unsaturated polyurethane prepolymers, or any mixture thereof.Illustrative polyesters with one or more incorporated vinylunsaturations can include, but are not limited to, methacrylate,acrylate modified or terminated polyesters, or any mixture thereof.

As noted above, the α,β-unsaturated carbonyl compound can be, but is notlimited to, an α,β-unsaturated aldehyde (e.g., an enal), anα,β-unsaturated ketone (e.g., an enone), an α,β-unsaturated carboxylicacid, an α,β-unsaturated ester, an α,β-unsaturated amide, anα,β-unsaturated acyl halide, an α,β-unsaturated acid anhydride, or anα,β-unsaturated imide. Illustrative α,β-unsaturated aldehydes caninclude, but are not limited to, crotonaldehyde, 3-methylcrotonaldehyde,methacrolein, tiglic aldehyde, isomers thereof, or any mixture thereof.Illustrative α,β-unsaturated ketones can include, but are not limitedto, methyl vinyl ketone, ethyl vinyl ketone, isomers thereof, or anymixture thereof. Illustrative α,β-unsaturated carboxylic acids caninclude, but are not limited to, maleic acid, itaconic acid, fumaricacid, glutaconic acid, citraconic acid, traumatic acid, muconic acid,aconitic acid, isomers thereof or any mixture thereof. Illustrativeα,β-unsaturated esters can include, but are not limited to, esters ofmaleic acid, itaconic acid, fumaric acid, glutaconic acid, citraconicacid, traumatic acid, muconic acid, aconitic acid, isomers thereof, orany mixture thereof. An illustrative α,β-unsaturated amide can include,but are not limited to, acrylamide. Illustrative α,β-unsaturated acylhalides can include, but are not limited to, acryloyl chloride,methacryloyl chloride, crotonoyl chloride, fumaryl chloride, itaconylchloride, sorbic chloride, isomers thereof, or any mixture thereof. Anillustrative α,β-unsaturated acid anhydride can include, but is notlimited to, maleic anhydride, an isomer thereof, or a mixture thereof.An illustrative α,β-unsaturated imide can include, but is not limitedto, maleimide, an isomer thereof, or a mixture thereof.

Other compounds having one or more pi-bonds (e.g., unsaturated bonds)that are capable of going through a radical chain reaction mechanism,but are also conjugated with an aromatic moiety, can include, but arenot limited to, vinyl aromatics, such as styrene, methylstyrenes, vinyltoluene, vinyl naphthalene, divinylbenzene (DVB), and vinylpyridine;methylstyrenes, such as α-methylstyrene and trans-β-methylstyrene; andany mixture thereof.

Illustrative unsaturated starch compounds having at least oneunsaturated and polymerizable olefinic group can be represented byFormula I below.

where R¹ can be hydrogen or an alkyl group. Suitable starches caninclude, but are not limited to, maize or corn, waxy maize, high amylosemaize, potato, tapioca, and wheat starch. Other starches such asgenetically engineered starches can include high amylose potato andpotato amylopectin starches. Suitable methods for preparing unsaturatedstarch compounds having at least one unsaturated and polymerizableolefinic group can include those discussed and described in U.S. Pat.No. 2,668,156.

The unsaturated prepolymer can include one or more monounsaturatedprepolymers, one or more polyunsaturated prepolymers, or any mixturethereof. In one or more embodiments, suitable polyunsaturatedprepolymers can include at least two sites of unsaturation, at leastthree sites of unsaturation, at least 4 sites of unsaturation, at least5 sites of unsaturation, at least 6 sites of unsaturation, or more. Inone or more embodiments, the unsaturated prepolymer can be unsaturatedpolyester prepolymers, unsaturated polyether prepolymers, unsaturatedpolyamide prepolymers, unsaturated polyurethane prepolymers, or anymixture thereof.

The unsaturated polyester prepolymer can be synthesized or produced byreacting one or more polyacids and one or more polyols with one another.For example, the unsaturated prepolymer can be produced via monoesterformation. In another example, the unsaturated polyester prepolymer canbe produced by reacting the polyacid and the polyol via a condensationreaction. As used herein, the term “polyacid” refers to compounds havingat least two reactive acid groups per molecule. The acid functionalitycan be a carboxylic acid, a sulfonic acid, or a combination thereof. Theterm “polyacid” can also refer to acid anhydrides, e.g., maleicanhydride. The term “polyacid” can also refer to compounds containing atleast one acid group per molecule and at least one acid anhydride groupper molecule, e.g., a maleated fatty acid. As used herein, the term“polyol” refers to compounds that contain two or more hydroxylfunctional groups.

In one or more embodiments, the one or more sites of unsaturation in theunsaturated polyester prepolymer can be directly introduced from thepolyacid and/or the polyol, e.g., at least one of the polyacid and thepolyol can include one or more sites of unsaturation. Said another way,the unsaturated polyester prepolymer can be produced by reacting one ormore unsaturated polyacids with one or more saturated polyols, reactingone or more unsaturated polyols with one or more saturated polyacids,and/or by reacting one or more unsaturated polyacids with one or moreunsaturated polyols. In one or more embodiments, the sites ofunsaturation in the unsaturated polyester prepolymer can be appended toan initial prepolymer formed by reacting the polyacid and the polyolwith one or more unsaturated compounds. In another example, theunsaturation sites of the unsaturated polyester prepolymer can beintroduced via at least one of the polyol and the poly acid, and anadditional unsaturated compound. Illustrative additional unsaturatedcompounds can include, but are not limited to, unsaturated alcohols,unsaturated acids, unsaturated epoxides, or any mixture thereof.

The polyacid and polyol components can be mixed, blended, or otherwisecombined with one another to produce a reaction mixture. The polyacidand polyol can be reacted under conditions sufficient to substantiallyreact the primary hydroxyl groups of the polyol with the polyacid, butinsufficient to cause reaction of the secondary hydroxyl groups of thepolyol with the polyacid to a substantial extent. As used herein, thephrase “substantially react the primary hydroxyl groups of the polyolwith the polyacid” means that at least 90% of the primary hydroxylgroups of the polyol are reacted with the polyacid. As used herein, thephrase “insufficient to cause reaction of the secondary hydroxyl groupsof the polyol with the polyacid to a substantial extent” means that lessthan 10% of the secondary hydroxyl groups of the polyol are reacted withthe polyacid. For example, the polyacid and the polyol can be combinedin a reaction vessel or container and heated to a temperature of about50° C., about 60° C., about 70° C., or about 80° C. to about 110° C.,about 125° C., about 140° C., or about 155° C. In another example, thepolyacid and the polyol can be heated to a temperature of about 60° C.to about 130° C., about 80° C. to about 115° C., about 100° C. to about150° C., or about 75° C. to about 135° C. The polyacid and the polyolcan be reacted with one another for a time of about 10 minutes, about 30minutes, about 1 hour, or about 2 hours to about 4 hours, about 6 hours,about 8 hours, or about 10 hours.

The progress of the reaction between the polyacid and the polyol can bemonitored via any suitable method. One method for monitoring the extentof the reaction between the polyacid and the polyol can be through theuse of infrared spectroscopy. For example, infrared spectroscopy candetect the presence of any unreacted polyacid. In one example, thereaction between the polyacid and the polyol can be carried out untilthe presence of the polyacid is no longer detected. It should be noted,however, that the unsaturated polyester prepolymer can include unreactedpolyacid and/or unreacted polyol.

The polyacid and the polyol can be combined with one another in anydesired ratio. For example, the polyol and the polyacid can be combinedwith one another at a molar ratio raging of about 1:5, about 1:4, orabout 1:2, to about 1:1, about 2:1, about 4:1, or about 6:1. In at leastone example, the amount of the polyacid combined with the polyol can besufficient to provide a ratio of reactive acid and/or anhydride group(s)to hydroxy groups of about 1:1 to about 2:1. In one or more embodiments,for each hydroxy group present in the polyol about 1 acid group, about 2acid groups, or about 3 acid groups can be present in the mixture of thepolyol and the polyacid.

The polyacid can be or include, but is not limited to, one or moreunsaturated and/or saturated aliphatic polyacids, one or more aromaticpolyacids, one or more cyclo-aliphatic polyacids, one or more acidanhydrides, or any mixture thereof. Suitable unsaturated aliphaticdiacids and saturated aliphatic diacids can include about 2 carbon atomsto about 12 carbon atoms, about 3 carbon atoms to about 10 carbon atoms,or about 4 carbon atoms to about 8 carbon atoms. Illustrativeunsaturated aliphatic diacids can include, but are not limited to,maleic acid, itaconic acid, fumaric acid, glutaconic acid, citraconicacid, traumatic acid, muconic acid, aconitic acid, or any mixturethereof. Illustrative saturated aliphatic diacids can include, but arenot limited to, oxalic acid, malonic acid, succinic acid, glutaric acid,adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, orany mixture thereof. Illustrative aromatic diacids can include, but arenot limited to, phthalic acid, isophthalic acid, terephthalic acid, orany mixture thereof. Illustrative cyclo-aliphatic diacids can include,but are not limited to, cyclobutanedicarboxylic acid,cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, isomersthereof, or any mixture thereof. Illustrative acid anhydrides caninclude, but are not limited to, phthalic anhydride, mellitic anhydride,pyromellitic anhydride, maleic anhydride, or any mixture thereof. In oneor more embodiments, the polyacid can also include one or moreunsaturated fatty acids reacted with any one or more of the polyacidsdiscussed and described above. For example, in at least one specificembodiment, the polyacid can be or include the Alder-Ene reactionproduct between one or more unsaturated fatty acids and maleicanhydride. Said another way, the polyacid can be or include one or moremaleated fatty acids.

Illustrative saturated polyols can include, but are not limited to,ethylene glycol, polyglycerol, hyperbranched polyglycerol, diethyleneglycol, triethylene glycol, polyethylene oxide (hydroxy terminated),glycerol, pentaerythritol, trimethylolpropane, diethanolamine,triethanolamine, ethyl diethanolamine, methyl diethanolamine, sorbitol,monosaccharides, such as glucose and fructose, disaccharides, such assucrose, and higher polysaccharides such as starch and reduced and/ormodified starches, dextrin, maltodextrin, polyvinyl alcohols,hydroxyethylcellulose, 1,4-cyclohexane diol, or any mixture thereof.Illustrative unsaturated polyols can include, but are not limited to,2-butene-1,4-diol, hydroxyl-terminated polybutadiene (HTPB), or anymixture thereof.

Illustrative unsaturated alcohols suitable for introducing, appending,or otherwise providing one or more sites of unsaturation in theunsaturated polyester prepolymer can include, but are not limited to,any one or more of the unsaturated polyols discussed and describedabove, allylic alcohols, unsaturated alcohols obtained via metathesisreaction of hydroxyl-substituted unsaturated fatty acid or fatty acidesters, or any mixture thereof. The preparation of unsaturated alcoholsvia metathesis reaction can be as discussed and described in U.S. Pat.No. 7,176,336. Illustrative unsaturated acids suitable for introducing,appending, or otherwise providing one or more sites of unsaturation inthe unsaturated polyester prepolymer can include, but are not limitedto, any one or more of the unsaturated polyacids discussed and describedabove, or any mixture thereof. Suitable unsaturated epoxides suitablefor introducing, appending, or otherwise providing one or more sites ofunsaturation in the unsaturated polyester prepolymer can include, butare not limited to, allyl glycidyl ether, 3,4-epoxy-1-butene,1,2-epoxy-5-hexene, any combination thereof or mixture thereof.

In one or more embodiments, one or more catalysts or unsaturatedpolyester prepolymer catalysts can optionally be present when thepolyacid and the polyol are reacted with one another. Suitable catalystscan include, but are not limited to, monobutyltin oxide, dibutyltinoxide, dibutyltin dilaurate, or any mixture thereof. The one or morecatalysts, if present, can be present in an amount of about 0.05 wt %,about 0.1 wt %, about 0.5 wt %, or about 1 wt % to about 2 wt %, about 3wt %, about 4 wt %, or about 5 wt %, based on the combined weight of thepolyacid and the polyol.

In one or more embodiments, the unsaturated polyester prepolymer can becombined with one or more reactive monomers in lieu of or in addition tothe water. Illustrative reactive monomers that can be combined with theunsaturated polyester prepolymer can include, but are not limited to,styrene, methyl styrene, chlorostyrene, vinyl toluene, divinyl benzene,vinyl acetate, acrylic acid, methacrylic acid, lower alkyl esters ofacrylic acid, lower alkyl esters of methacrylic acid, diallyl phthalate,vegetable oils, e.g., linseed oil, soy bean oil, sunflower oil, tungoil, or any mixture thereof. If the unsaturated polyester prepolymer iscombined with one or more reactive monomers, the amount of the one ormore reactive monomers can be about 1 wt %, about 5 wt %, about 10 wt %,about 15 wt %, or about 20 wt % to about 40 wt %, about 45 wt %, about50 wt %, about 55 wt %, or about 60 wt %, based on the combined weightof the one or more reactive monomers and the unsaturated polyesterprepolymer.

The unsaturated polyamide prepolymers can be produced by reacting one ormore polyamines with one or more polyacids. The unsaturated polyamideprepolymers can also be produced by reacting one or more polyamines withone or more esters. In one or more embodiments, the one or more sites ofunsaturation in the unsaturated polyamide prepolymer can be directlyintroduced from the polyacid and/or the polyamine, e.g., at least one ofthe polyacid and the polyamine can include one or more sites ofunsaturation. Said another way, the unsaturated polyamide prepolymer canbe produced by reacting one or more unsaturated polyacids with one ormore saturated polyamines, reacting one or more unsaturated polyamineswith one or more saturated polyacids, and/or by reacting one or moreunsaturated polyacids with one or more unsaturated polyamines. In one ormore embodiments, the sites of unsaturation in the unsaturated polyamideprepolymer can be appended to an initial prepolymer formed by reactingthe polyacid and the polyamine with one or more unsaturated compounds.In another example, the unsaturation sites of the unsaturated polyamideprepolymer can be introduced via at least one of the polyamine and thepoly acid, and an additional unsaturated compound. Illustrativeadditional unsaturated compounds can include, but are not limited to,unsaturated alcohols, unsaturated acids, unsaturated epoxides, or anymixture thereof.

The polyacid and polyamine components can be mixed, blended, orotherwise combined with one another to produce a reaction mixture. Thereaction mixture can be reacted under conditions sufficient to react thepolyacid with the polyamine to produce the unsaturated polyamideprepolymer. For example, the polyacid and the polyamine can be combinedin a reaction vessel or container and heated to a temperature of about50° C., about 60° C., about 70° C., or about 80° C. to about 110° C.,about 125° C., about 140° C., or about 155° C. In another example, thepolyacid and the polyamine can be heated to a temperature of about 60°C. to about 130° C., about 80° C. to about 115° C., about 100° C. toabout 150° C., or about 75° C. to about 135° C. The polyacid and thepolyamine can be reacted with one another for a time of about 10minutes, about 30 minutes, about 1 hour, or about 2 hours to about 4hours, about 6 hours, about 8 hours, or about 10 hours. Polyamides canalso be produced or obtained via transamidation.

The progress of the reaction between the polyacid and the polyamine canbe monitored via any suitable method. One method for monitoring theextent of the reaction between the polyacid and the polyamine can bethrough the use of infrared spectroscopy. For example, infraredspectroscopy can detect the presence of any unreacted polyacid. In oneexample, the reaction between the polyacid and the polyamine can becarried out until the presence of the polyacid is no longer detected. Itshould be noted, however, that the unsaturated polyamide prepolymer caninclude unreacted polyacid and/or unreacted polyamine.

The polyacid and the polyamine can be combined with one another in anydesired ratio. For example, the polyamine and the polyacid can becombined with one another at a molar ratio of about 1:5, about 1:4, orabout 1:2, to about 1:1, about 2:1, about 4:1, or about 6:1. In at leastone example, the amount of the polyacid combined with the polyamine canbe sufficient to provide a ratio of reactive acid and/or anhydridegroup(s) to amine groups of about 1:1 to about 2:1. For example, foreach amine group present in the polyamine about 1 acid group, about 2acid groups, or about 3 acid groups can be present in the mixture of thepolyamine and the polyacid.

Suitable polyacids can include those discussed and described above orelsewhere herein. Illustrative saturated polyamines can include, but arenot limited to, ethylenediamine, propylenediamine, hexamethylenediamine,diethylenetriamine (DETA), triethylenetetramine (TETA),tetraethylenepentamine (TEPA), 1,3-propanediamine, 1,4-butanediamine,hyperbranched polyethyleneimine, or any mixture thereof. Illustrativeunsaturated polyamines can include those represented by the followinggeneral Formula II below:

where R² and R³ can independently be an organic group having 1 carbonatom to about 24 carbon atoms, e.g., an alkyl group containing 1 carbonatom to about 12 carbon atoms, and n can be an integer of 2 to about 12.Illustrative unsaturated polyamines having Formula II can be preparedaccording to the methods discussed and described in U.S. Pat. No.3,773,833.

The unsaturated polyether prepolymers can be produced by polymerizationof allyl glycidyl ether (AGE) to form poly(allyl glycidyl ether) (PAGE).The prepolymer can include pendant allyl groups. Suitable reactionconditions for producing the unsaturated polyether prepolymer caninclude those discussed and described in Lee, B. F. et al., “Poly(AllylGlycidyl Ether)-A Versatile and Functional Polyether Platform,” Journalof Polymer Science Part A: Polymer Chemistry, Vol. 49, August 2011, pp.4498-4504. The copolymerization reaction of AGE with other monomers canbe as discussed and described in Sunder, A. et al., “Copolymers ofGlycidol and Glycidyl Ethers: Design of Branched Polyether Polyols byCombination of Latent Cyclic AB2 and ABR Monomers,” Macromolecules, Vol.33, September 2000, pp. 7682-7692, and Erberich, M. et al.,“Polyglycidols with Two Orthogonal Protective Groups: Preparation,Selective Deprotection, and Functionalization,” Macromolecules, Vol. 40,April 2007, pp. 3070-3079.

The unsaturated polyurethane prepolymers can be produced by reacting oneor more polyisocyanates with one or more compounds containing activehydrogen functionality. Moieties that provide active hydrogenfunctionality can include, but are not limited to, hydroxyl groups,mercaptan groups, amine groups, and carboxyl groups. For example, one ormore polyols can be reacted with the polyisocyanate to produce theunsaturated polyurethane prepolymer.

Suitable polyisocyanates can include, but are not limited to,hexamethylene diisocyanate, toluene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), m-phenylene and p-phenylene diisocyanates,bitolylene diisocyanate, cyclohexane diisocyanate (CHDI),bis-(isocyanatomethyl) cyclohexane (H₆XDI), dicyclohexylmethanediisocyanate (H₁₂MDI), dimer acid diisocyanate (DDI), trimethylhexamethylene diisocyanate, lysine diisocyanate and its methyl ester,methyl cyclohexane diisocyanate, 1,5-napthalene diisocyanate, xylyleneand xylene diisocyanate and methyl derivatives thereof, polymethylenepolyphenyl isocyanates, chlorophenylene-2,4-diisocyanate, polyphenylenediisocyanates available commercially as, for example, Mondur MR orMondur MRS, isophorone diisocyanate (IPDI), hydrogenated methylenediphenyl isocyanate (HMDI), tetramethyl xylene diisocyanate (TMXDI),hexamethylene diisocyanate (HDI), or oligomer materials of thesematerials such as a trimer of IPDI, HDI or a biuret of HDI, and thelike, and mixtures thereof. Triisocyanates and high-functionalisocyanates can also be used. Aromatic and aliphatic diisocyanates, forexample, biuret and isocyanurate derivatives can be used.

Suitable polyols for reacting with the polyisocyanates can include, butare not limited to, polyether polyols (e.g., block polyethylene andpolypropylene oxide homo- and co-polymers in molecular weight of about300 to about 3,000), alkylated polyols (e.g., polytetramethylene etherglycols), caprolactone-based polyols, and the like. In one or moreembodiments, the reactants for making the polyurethane prepolymer can beor include mixtures of aliphatic and aromatic polyols, or amulti-functional, active hydrogen-bearing polymer. As such, in additionto or in lieu of polyether polyols, the hydroxyl-functional componentcan include derivatives of acrylates, esters, vinyls, and castor oils,as well as polymers and mixtures thereof.

Isocyanate equivalents can predominate over active hydrogen equivalentsin the polyisocyanate/polyol reaction mixture to produce a prepolymerthat can include residual isocyanate groups. The isocyanate and thepolyol can be combined with one another in any desired ratio. Forexample, the isocyanate and the polyol can be combined with one anotherat a molar ratio of about 1:5, about 1:4, or about 1:2, to about 1:1,about 2:1, about 4:1, or about 5:1. Suitable reaction conditions forproducing the unsaturated polyurethane prepolymer can include thosediscussed and described in Heiss, et al., “Influence of Acids and Baseson Preparation of Urethane Polymers,” Industrial and EngineeringChemistry, Vol. 51, No. 8, August 1959, pp. 929-934. Depending upon thereaction conditions used (such as, for example, temperature and thepresence of strong acids or bases, and catalysts), the reaction may leadto the formation of ureas, allophanates, biurets, or isocyanates.

Suitable amine group containing compounds that can be reacted with thepolyisocyanates can include, but are not limited to, unsaturatedpolyamines represented by the general Formula II discussed and describedabove. Suitable carboxyl group containing compounds that can be reactedwith the polyisocyanates can include, but are not limited to,unsaturated aliphatic diacids. Illustrative unsaturated aliphaticdiacids can include, but are not limited to, maleic acid, itaconic acid,fumaric acid, glutaconic acid, citraconic acid, traumatic acid, muconicacid, aconitic acid, or any mixture thereof.

In one or more embodiments, one or more catalysts or unsaturatedpolyurethane prepolymer catalysts can be used to accelerate the rate ofreaction of the polyisocyanate and the polyol to produce the unsaturatedpolyurethane prepolymer. Suitable catalysts can include, but are notlimited to, dibutyl tin dilaurate. In one or more embodiments, one ormore inhibitors can be used to slow the cross-linking reaction. Suitableinhibitors can include, but are not limited to, benzoyl chloride andmonophenyldichlorophosphate.

In one or more embodiments, the unsaturated prepolymer, can have a pH ofabout 0.5, about 2, about 3, or about 4 to about 7, about 7.5, about 8,about 8.5, or about 9. For example, the unsaturated polyester prepolymercan have a pH of about 1.5 to about 9, about 2.5 to about 7, about 1 toabout 5, about 5 to about 8, or about 3 to about 6.

In one or more embodiments, the unsaturated prepolymer can be combinedwith water to produce a water and unsaturated prepolymer mixture. Forexample, water can be mixed, blended, or otherwise combined with theunsaturated prepolymer to produce the water and unsaturated prepolymermixture. The unsaturated prepolymer can be soluble in water. Theunsaturated prepolymer can be dissolved in water to produce an aqueousunsaturated prepolymer solution. The unsaturated prepolymer can becombined with water to form an aqueous suspension, emulsion, ordispersion. The amount of the water, combined with the unsaturatedprepolymer can be about 1 wt %, about 5 wt %, about 10 wt %, about 15 wt%, about 20 wt %, about 25 wt %, about 30 wt %, or about 35 wt % toabout 50 wt %, about 55 wt %, about 60 wt %, about 65 wt %, about 70 wt%, or about 75 wt %, based on the combined weight of the water and theunsaturated prepolymer. The unsaturated polyester prepolymer combinedwith water can have a viscosity of about 20 cP, about 100 cP, 1,000 cP,about 5,000 cP, or about 10,000 cP to about 50,000 cP, about 100,000 cP,about 200,000 cP, or about 300,000 cP at a temperature of about 25° C.The viscosity of the unsaturated polyester prepolymer can be determinedusing a viscometer at a temperature of about 25° C. For example, asuitable viscometer can be the model DV-II+ viscometer, available fromBrookfield Engineering Laboratories, with a small sample adapter, forexample, a number 3 spindle. The small sample adapter can allow thesample to be cooled or heated by the chamber jacket to maintain thetemperature of the sample surrounding the spindle at a temperature ofabout 25° C.

Polyamidoamines and unsaturated glycidyl ethers suitable for producingone or more products formed by reacting the polyamidoamine and theunsaturated glycidyl ether can widely vary. The polyamidoamine can be areaction product of a polyamine and a dicarboxylic acid. In someexample, the polyamine can be dimethylenetriamine, diethylenetriamine,triethylenetetramine, tripropylenetetramine, tetraethylenepentamine,pentaethylenehexamine, or any mixture thereof. The dicarboxylic acid canbe glutaric acid, adipic acid, azelaic acid, malonic acid, suberic acid,sebacic acid, succinic acid, oxalic acid, pimelic acid, derivativesthereof, or any mixture thereof. The epihalohydrin can beepichlorohydrin, epibromohydrin, epifluorohydrin, epiiodohydrin, or anymixture thereof.

Illustrative unsaturated glycidyl ethers can be represented by generalFormula III:

where R⁴ can be an ethylenically unsaturated radical such as vinyl,allyl, alkenyl, and the like. Suitable glycidyl ethers can include, butare not limited to, vinyl glycidyl ether, isopropenyl glycidyl ether,oleyl glycidyl ether, allyl glycidyl ether, p-vinylbenzyl glycidylether, o-allyl phenyl glycidyl ether, butenyl glycidyl ether,4-vinylcyclohexyl glycidyl ether, abietylglycidyl ether,cyclohexeneylmethyl glycidyl ether, methallyl glycidyl ether, or anymixture thereof.

Suitable reaction products produced by reacting one or morepolyamidoamines and one or more unsaturated glycidyl ethers and methodsfor making the reaction products can be as discussed and described inU.S. Pat. Nos. 2,864,775 and 3,280,054.

The product(s) formed by reacting the polyamidoamine(s) and theunsaturated glycidyl ether(s) can act or serve as active reducers. Asused herein, the term “active reducer” refers to compounds that canparticipate in a cross-linking reaction, e.g., have double bonds, andalso have one or more groups that can be oxidized, e.g., a tertiaryamine.

Any suitable free radical precursor or combination of free radicalprecursors can be used to produce the binder composition. The freeradical precursor can be a solid, liquid, gas, or multi-phase. As usedherein, the phrase “free radical precursor” refers to any compound ormixture of compounds that can generate radicals when subjected topredetermined conditions. For example, the free radical precursor can bea compound or mixture of compounds that can generate radicals whenheated to a predetermined temperature. For example, if the free radicalprecursor includes an oxidant, e.g., an inorganic oxidant such ashydrogen peroxide, and a catalyst or free radical precursor catalyst,e.g., a transition metal catalyst, the free radical precursor cangenerate radicals when the oxidant is subjected to reaction with thecatalyst. As such, in one or more embodiments, the free radicalprecursor can include one or more oxidants and one or more catalysts.

Illustrative free radical precursors can include, but are not limitedto, inorganic and/or organic peroxy compounds, ozonides, halogencontaining oxidants, or any mixture thereof. Illustrative inorganicperoxy compounds can include, but are not limited to, hydrogen peroxide,hydrogen peroxide generating compounds, e.g., alkali metal salts ofpercarbonate, perborate, peroxysulfate, peroxyphosphate, and/orperoxysilicate, and/or corresponding weak acids. Illustrative organicperoxy compounds can include, but are not limited, to t-butyl peroxide,benzoyl peroxide, peroxy carboxylic acids, e.g., peracetic acid and/orperbenzoic acid, hydroperoxides, e.g., t-butyl hydroperoxide, or mixturethereof. Illustrative halogen containing oxidants can include, but arenot limited to, alkali metal chlorite, alkali metal hypochlorite,chlorine dioxide, and/or a chloro sodium salt of cyanuric acid. Anillustrative ozonide can include, but is not limited to,dimethyloxirane. An illustrative azo compound can include, but is notlimited to, azobisisobutyronitrile (AIBN). In one or more embodiments,the free radical precursor can be or include one or more inorganicoxidants. In one or more embodiments, the free radical precursor can beor include one or more inorganic peroxy compounds. In one or moreembodiments, the free radical precursor can be or include hydrogenperoxide.

If the one or more oxidants are present as the free radical precursor oras a component of the free radical precursor, the one or more oxidantscan be present in an amount of about 1 wt %, about 3 wt %, about 5 wt %,about 7 wt %, about 9 wt %, about 10 wt %, about 12 wt %, about 15 wt %,about 20 wt %, about 25 wt %, about 30 wt %, about 35 wt %, or about 40wt % to about 60 wt %, about 65 wt %, about 70 wt %, about 75 wt %,about 80 wt %, about 85 wt %, about 90 wt %, about 95 wt %, or about 99wt %, based on the weight of the unsaturated compound. For example, theamount of the free radical precursor in the binder composition can beabout 7 wt % to about 99 wt %, about 10 wt % to about 80 wt %, about 15wt % to about 70 wt %, about 17 wt % to about 66 wt %, about 10 wt % toabout 45 wt %, about 35 wt % to about 75 wt %, about 15 wt % to about 25wt %, about 20 wt % to about 35 wt %, about 30 wt % to about 50 wt %,about 35 wt % to about 60 wt %, or about 45 wt % to about 80 wt %, basedon the weight of the unsaturated compound. In another example, theamount of the free radical precursor in the binder composition can bepresent in an amount of at least 3 wt %, at least 5 wt %, at least 6 wt%, at least 7 wt %, at least 8 wt %, at least 9 wt %, at least 10 wt %,at least 15 wt %, at least 20 wt %, at least 25 wt % at least 20 wt %,at least 35 wt %, at least 40 wt %, or at least 45 wt % to about 50 wt%, about 55 wt %, about 60 wt %, about 65 wt %, about 70 wt %, about 75wt %, about 80 wt %, about 85 wt %, about 90 wt %, or about 95 wt %,based on the weight of the unsaturated compound. In another example, theamount of the free radical precursor in the binder composition can beless than 95 wt %, less than 90 wt %, less than 85 wt %, less than 80 wt%, less than 75 wt %, less than 70 wt %, less than 60 wt %, less than 55wt %, less than 50 wt %, less than 45 wt %, or less 40 wt % and greaterthan 2 wt %, greater than 5 wt %, greater than 6 wt %, greater than 7 wt%, greater than 8 wt %, greater than 9 wt %, greater than 10 wt %,greater than 15 wt %, greater than 20 wt %, or greater than 25 wt %,based on the weight of the unsaturated compound.

The free radical precursor can be combined with one or more liquidmediums. For example, the free radical precursor can be or include anaqueous solution of hydrogen peroxide. The concentration of free radicalprecursor, e.g., hydrogen peroxide combined with a liquid medium such aswater, can be about 1 wt %, about 3 wt %, about 5 wt %, about 10 wt %,about 15 wt %, about 20 wt %, about 25 wt %, or about 30 wt % to about50 wt %, about 60 wt %, about 70 wt %, about 80 wt %, about 90 wt %, orabout 98 wt %, based on the combined weight of the free radicalprecursor and the liquid medium.

If the catalyst or free radical precursor catalyst is present in thebinder composition as a component of the free radical precursor, thecatalyst can be combined with the other component(s) of the free radicalprecursor, e.g., an oxidant, to any other component of the bindercomposition, or any combination thereof to produce the bindercomposition. The catalyst can also be referred to as an initiator, apromoter, a reducer, and/or an accelerator. Suitable catalysts can be orinclude, but are not limited to, metal ions, tertiary amines, polymerictertiary amines, phosphates, bisulfites, metabisulfites,tetraacetylethylenediamine, cyanamides, ultraviolet light, or anymixture thereof. In one or more embodiments, in addition to or in lieuof contacting the lignocellulose substrates with a free radicalprecursor and/or catalyst, ultrasonic waves, photo-Fenton and/orelectro-Fenton reactions (in situ generation of hydroxyl radicals byradiation or electric currents) can be used. In one or more embodiments,the catalyst can be or include one or more transition metals withcoordinated Lewis bases.

Illustrative metal ions can include, but are not limited to, metal ionsof iron, copper, manganese, tungsten, molybdenum, or any mixturethereof. The metal can be in the form of an oxide. The metal can be inthe form of a salt or complex, e.g., bound to one or more complexingagents or compounds. Illustrative ions or complexing compounds caninclude, but are not limited to, cyanide (CN⁻), sulfate (SO₄ ²⁻),ethylenediaminetetraacetic acid (EDTA), ethylenediamine-N,N′-disuccinicacid (EDDS), ethyleneglycol bis(2-aminoethylether)-N,N,N′,N′-tetraaceticacid (EGTA), diethylenetriaminepentaacetic acid (DTPA),trans-1,2-diaminocyclohexane tetraacetic acid (CDTA), iminodisuccinate(IDS), nitrilotriacetic acid (NTA), or any mixture thereof. Othercomplexing compounds can include phosphates, or complexing agents basedon phosphonic acid, oxalic acid, ascorbic acid, nitrilo acetate, gallicacid, fulvic acid, or polyoxomethalates.

The metal ions can include compounds or complexes containing iron ions(e.g., Fe²⁺ or Fe³⁺), such as iron(II) sulfate, iron(II) oxide,iron(III) sulfate, iron(III) oxide. Other iron ion containing catalystcan include, but are not limited to, ferricyanide ([Fe(CN)₆]³⁻),ferrocyanide ([Fe(CN)₆]⁴⁻), and/or nitroprusside ([Fe(CN)₅NO]²⁻). Forexample, the catalyst can be or include, but is not limited to,potassium ferricyanide (K₃[Fe(CN)₆]), potassium ferrocyanide(K₄[Fe(CN)₆]), ammonium ferricyanide hydrate ((NH₄)₃[Fe(CN)₆].xH₂O),ammonium ferrocyanide hydrate ((NH₄)₄[Fe(CN)₆].xH₂O), sodiumferricyanide decahydrate (Na₃[Fe(CN)₆].10H₂O), sodium ferrocyanidedecahydrate (Na₄[Fe(CN)₆].10H₂O), sodium nitroprusside dihydrate(Na₂[Fe(CN)₅NO].2H₂O). Other suitable catalyst that contain iron caninclude, but are not limited to, Fe[EDTA], Fe[EDDS], Fe[DTPA], Fe[EGTA],Fe[CDTA], Fe[IDS], or any mixture thereof. In at least one specificembodiment, the catalyst can include ferricyanide, e.g., potassiumferricyanide, a complex of iron (e.g., ferric and/or ferrous) andethylenediaminetetraacetic acid (EDTA), a complex of iron (e.g., ferricand/or ferrous) and (S,S)-ethylenediamine-N,N′-disuccinic acid((S,S)-EDDS), a complex of iron (e.g., ferric and/or ferrous) and(R,R)-ethylenediamine-N,N′-disuccinic acid ((R,R)-EDDS), a complex ofiron (e.g., ferric and/or ferrous) and(R,S)-ethylenediamine-N,N′-disuccinic acid ((R,S)-EDDS), a complex ofiron (e.g., ferric and/or ferrous) and diethylenetriaminepentaaceticacid (DTPA), a complex of iron (e.g., ferric and/or ferrous) andtrans-1,2-diaminocyclohexane tetraacetic acid (CDTA), a complex of iron(e.g., ferric and/or ferrous) and iminodisuccinate (IDS), hydratesthereof, or any mixture thereof.

Tertiary amines can be represented by the general formula NR⁵R⁶R⁷, whereeach R⁵, R⁶, and R⁷ can independently be selected from alkyls,cycloalkyls, heterocycloalkyls, aryls, heteroaryls, and substitutedaryls. The alkyl can include branched or unbranched alkyls having 1carbon atom to about 15 carbon atoms or 1 carbon atom to about 8 carbonatoms. Illustrative alkyls can include one or more, but are not limitedto, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl,pentyl, hexyl, ethylhexyl, and isomers thereof. The cycloalkyls caninclude 3 carbon atoms to about 7 carbon atoms. Illustrative cycloalkylscan include, but are not limited to, cyclopentyl, substitutedcyclopentyl, cyclohexyl, and substituted cyclohexyl. The term “aryl”refers to an aromatic substituent containing a single aromatic ring ormultiple aromatic rings that are fused together, linked covalently, orlinked to a common group such as a methylene or ethylene moiety. Morespecific aryl groups can include one aromatic ring or two or three fusedor linked aromatic rings, e.g., phenyl, naphthyl, biphenyl, anthracenyl,phenanthrenyl, and the like. The aryl substituents can include 1 carbonatom to about 20 carbon atoms. The term “heteroatom-containing,” as in a“heteroatom-containing cycloalkyl group,” refers to a molecule ormolecular fragment in which one or more carbon atoms is replaced with anatom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus,boron, or silicon. Similarly, the term “heteroaryl” refers to an arylsubstituent that is heteroatom-containing. The term “substituted,” as in“substituted aryls,” refers to a molecule or molecular fragment in whichat least one hydrogen atom bound to a carbon atom is replaced with oneor more substituents that is/are a functional group(s) such as hydroxyl,alkoxy, alkylthio, phosphino, amino, halo, and silyl. Illustrativetertiary amines can include, but are not limited to, trimethylamine,triethylamine, triethanolamine, or any mixture thereof. Illustrativepolymeric tertiary amines can include, but are not limited to,poly(N-methyldiallyl amine), poly(N-dimethylvinyl amine), copolymers ofN-dimethylvinyl amine, or any mixture thereof.

Illustrative phosphates can be or include, but are not limited to,potassium phosphate, sodium phosphate, ammonium phosphate, or anymixture thereof. Illustrative bisulfites can include sodium bisulfite.Illustrative metabisulfites can be or include, but are not limited to,sodium metabisulfite, potassium metabisulfite, or a combination ormixture thereof. Illustrative cyanamides can include, but are notlimited to, cyanamide, calcium cyanamide, sodium hydrogen cyanamide, orany mixture thereof.

The catalyst, if combined with a liquid medium, can have a totalconcentration of solids of about 0.001 wt % to about 99.9 wt %. Forexample, if the catalyst is combined with a liquid medium, the mixtureof the catalyst and liquid medium can have a concentration of solids ofabout 0.1 wt %, about 0.5 wt %, about 1 wt %, or about 2 wt % to about 4wt %, about 5 wt %, about 6 wt %, about 7 wt %, or about 8 wt %, basedon the combined weight of the catalyst and the liquid medium.

The amount of catalyst present in the binder composition can widelyvary. For example, the amount of catalyst in the binder composition canbe about 0.01 wt %, about 0.1 wt %, about 0.5 wt %, about 1 wt %, orabout 3 wt % to about 8 wt %, about 10 wt %, about 12 wt %, about 14 wt%, about 17 wt %, or about 20 wt %, based on the combined weight of theunsaturated compound and the free radical precursor, where the catalystis a component or part of the free radical precursor. In anotherexample, the amount of catalyst in the binder composition can be about 1wt % to about 5 wt %, about 3 wt % to about 13 wt %, about 0.1 wt % toabout 9 wt %, about 1 wt % to about 7 wt %, about 7 wt % to about 15 wt%, or about 0.2 wt % to about 15 wt %, based on the combined weight ofthe unsaturated compound and the free radical precursor, where thecatalyst is a component or part of the free radical precursor. Inanother example, when the free radical precursor includes both thecatalyst and an oxidant, e.g., an inorganic oxidant, the amount ofcatalyst in the binder composition can be about 0.0001 wt %, about 0.001wt %, about 0.01 wt %, about 0.1 wt %, about 0.13 wt %, or about 0.15 wt% to about 0.17 wt %, about 0.2 wt %, about 0.23 wt %, about 0.25 wt %,about 0.27 wt %, about 0.3 wt %, about 0.35 wt %, about 0.4 wt %, about0.5 wt %, about 1 wt %, about 2 wt %, about 3 wt %, about 4 wt %, about5 wt %, about 6 wt %, about 7 wt %, about 8 wt %, about 9 wt %, or about10 wt %, based on the combined weight of the unsaturated compound, thefree radical precursor, and the oxidant. In another example, the amountof catalyst in the binder composition can be about 0.01 wt % to about 2wt %, about 0.17 wt % to about 0.37 wt %, about 0.19 wt % to about 0.31wt %, about 0.2 wt % to about 0.29 wt %, about 0.05 wt % to about 1.5 wt%, or about 0.2 wt % to about 2 wt %, about 0.5 wt % to about 3.5 wt %,about 1.3 wt % to about 2 wt %, about 0.8 wt % to about 2.4 wt %, orabout 1.4 wt % to about 1.7 wt %, based on the combined weight of theunsaturated compound, free radical precursor, and oxidant.

The binder composition can have a viscosity of about 1 cP, about 20 cP,about 100 cP, 1,000 cP, about 5,000 cP, or about 10,000 cP to about50,000 cP, about 100,000 cP, about 200,000 cP, or about 300,000 cP at atemperature of 25° C. For example, the binder composition can have aviscosity of about 20 cP to about 50,000 cP, about 500 cP to about25,000 cP, about 15,000 cP to about 45,000 cP, or about 3,000 cP toabout 40,000 cP at a temperature of about 25° C. The viscosity of thebinder composition and/or any other composition discussed and describedherein can be determined using a viscometer at a temperature of about25° C. For example, a suitable viscometer can be the model DV-II+viscometer, available from Brookfield Engineering Laboratories, with asmall sample adapter, for example, a number 3 spindle. The small sampleadapter can allow the sample to be cooled or heated by the chamberjacket to maintain the temperature of the sample surrounding the spindleat a temperature of about 25° C.

The pH of the binder composition can be acidic, neutral, or basic. Forexample, the pH of the binder composition can be about 0.5, about 2,about 3, or about 4 to about 7, about 7.5, about 8, about 8.5, or about9. For example, the binder composition can have a pH of about 1.5 toabout 9, about 2.5 to about 7, about 1 to about 5, about 5 to about 8,or about 3 to about 6. The pH of the binder composition can be adjustedto any desired pH by combining one or more base compounds, one or moreacid compounds, or a combination of one or more base compounds and oneor more acid compounds therewith.

Illustrative base compounds that can be used to adjust the pH of thebinder composition can include, but are not limited to, hydroxides,carbonates, ammonia, amines, or any mixture thereof. Illustrativehydroxides can include, but are not limited to, sodium hydroxide,potassium hydroxide, ammonium hydroxide (e.g., aqueous ammonia), lithiumhydroxide, cesium hydroxide, or any mixture thereof. Illustrativecarbonates can include, but are not limited to, sodium carbonate, sodiumbicarbonate, potassium carbonate, ammonium carbonate, or any mixturethereof. Illustrative amines can include, but are not limited to,trimethylamine, triethylamine, triethanolamine, diisopropylethylamine(Hunig's base), pyridine, 4-dimethylaminopyridine (DMAP),1,4-diazabicyclo[2.2.2]octane (DABCO), or any mixture thereof.

Illustrative acid compounds that can be used to adjust the pH of thebinder composition can include, but are not limited to, one or moremineral acids, one or more organic acids, one or more acid salts, or anymixture thereof. Illustrative mineral acids can include, but are notlimited to, hydrochloric acid, nitric acid, phosphoric acid, sulfuricacid, or any mixture thereof. Illustrative organic acids can include,but are not limited to, acetic acid, formic acid, citric acid, oxalicacid, uric acid, lactic acid, or any mixture thereof. Illustrative acidsalts can include, but are not limited to, ammonium sulfate, sodium,sodium bisulfate, sodium metabisulfite, or any mixture thereof.

As used herein, the term “lignocellulose” refers to a material thatincludes lignin and cellulose, hemicelluose, or a combination ofcellulose and hemicelluloses. The lignocellulose substrates can be orinclude, but is not limited to, straw, hemp, sisal, cotton stalk, wheat,bamboo, sabai grass, rice straw, banana leaves, paper mulberry (e.g.,bast fiber), abaca leaves, pineapple leaves, esparto grass leaves,fibers from the genus Hesperaloe in the family Agavaceae jute, saltwater reeds, palm fronds, flax, ground nut shells, hardwoods, softwoods,recycled fiberboards such as high density fiberboard, medium densityfiberboard, low density fiberboard, oriented strand board,particleboard, animal fibers (e.g., wool or hair), recycled paperproducts (e.g., newspapers, cardboard, cereal boxes, and magazines), orany mixture thereof. Suitable woods can include softwoods and/orhardwoods. Illustrative types of wood can include, but are not limitedto, alder, ash, aspen, basswood, beech, birch, cedar, cherry,cottonwood, cypress, elm, fir, gum, hackberry, hickory, maple, oak,pecan, pine, poplar, redwood, sassafras, spruce, sycamore, walnut,willow, or any mixture thereof.

The starting material, from which the lignocellulose substrates can beor can be derived from, can be shaped, reduced, or otherwise formed tothe appropriate dimensions by various processes such as hogging,grinding, hammer milling, tearing, shredding, and/or flaking. Otherprocesses for producing the substrates can include skiving, cutting,slicing, and/or sawing. Suitable forms of the lignocellulose substratescan include, but are not limited to, chips, flakes, wafers, fibers,shavings, sawdust or dust, veneer, or the like. Other suitablelignocellulose substrates can include, but are not limited to, woodchips, wood fibers, wood flakes, wood strands, wood wafers, woodshavings, wood particles, wood veneer, or any mixture thereof.

The particular configuration of the substrates can be based, at least inpart, on the desired product. For example, particulates such as chips,fibers, shavings, sawdust or dust, or the like can be used for producingparticleboards, fiberboards, and the like. The substrates can have alength of about 0.05 mm, about 0.1 mm, about 0.2 mm to about 1 mm, about5 mm, about 10 mm, about 20 mm, about 30 mm, about 40 mm, about 50 mm,or about 100 mm. In another example, veneers, e.g., layers or sheets ofwood, can be used for producing plywood, laminated veneer lumber, andthe like. The veneers can have a thickness of about 0.8 mm, about 0.9mm, about 1 mm, about 1.1 mm or about 1.2 mm to about 3 mm, about 4 mm,about 5 mm, about 6 mm, about 7 mm, about 8 mm, about 9 mm, or about 10mm.

The lignocellulose substrates can include liquid on, about, and/orwithin the substrates. For example, the lignocellulose substrates canhave a liquid concentration, e.g., a moisture content, of about 1 wt %,about 2 wt %, about 3 wt %, about 4 wt %, or about 5 wt % to about 7 wt%, about 8 wt %, about 9 wt %, about 10 wt %, about 11 wt %, or about 12wt % based on a dry weight of the lignocellulose substrate. In anotherexample, the lignocellulose substrates can have a liquid concentrationof about 1 wt % to about 10 wt %, about 2 wt % to about 4 wt %, about 2wt % to about 3 wt %, about 3 wt % to about 6 wt %, about 5 wt % toabout 10 wt %, about 6 wt % to about 8 wt %, or about 4 wt % to about 9wt %. The lignocellulose substrates can be fresh, e.g., not treated ordried, or dried and/or treated. For example, the lignocellulosesubstrates and/or the starting material from which the lignocellulosesubstrates were derived can be at least partially dried. In anotherexample, the lignocellulose substrates can be washed and/or leached withan aqueous medium such as water.

Returning to the mixture, in one or more embodiments, the components ofthe binder composition can independently be added to or otherwisecombined with the lignocellulose substrates to produce the mixture orresinated mixture. For example, the compound having two or moreunsaturated carbon-carbon bonds can be combined with the lignocellulosesubstrates to produce an intermediate mixture. The free radicalprecursor can be combined with the intermediate mixture to produce themixture or resinated furnish. In another example, the free radicalprecursor can be combined with the lignocellulose substrates to producethe intermediate mixture and the compound having two or more unsaturatedcarbon-carbon bonds can be combined with the intermediate mixture toproduce the mixture or resinated furnish. In another example, thecompound having two or more unsaturated carbon-carbon bonds and the freeradical precursor can be combined, e.g., added to, the lignocellulosesubstrates simultaneously to produce the mixture or resinated furnish.Similarly, if the free radical precursor includes two or morecomponents, e.g., an oxidant and a catalyst, the catalyst can becombined with the lignocellulose substrates as a mixture with theoxidant, independently with the lignocellulose substrates, with theunsaturated compound, or any combination thereof.

The components of the mixture can be contacted with one another via anysuitable method. For example, the lignocellulose substrates can be in avessel or other container and the free radical precursor, unsaturatedcompound, and/or catalyst can be sprayed onto the lignocellulosesubstrates. In another example, free radical precursor and unsaturatedcompound can be poured or brushed onto the lignocellulose substrates. Inanother example, the lignocellulose substrates can be directed,transported, introduced, or otherwise conveyed into a vessel alreadycontaining any one or more of the other components of the bindercomposition. Said another way, the lignocellulose substrates can bedipped, soaked, or otherwise contacted with the free radical precursor,the unsaturated prepolymer, or any mixture thereof.

The amount of the unsaturated compound in the mixture can widely vary.For example, the amount of the unsaturated compound in the mixture canbe about 0.01 wt % to about 50 wt %, based on the dry weight of thelignocellulose substrates. In another example, the amount of theunsaturated compound in the mixture can be about 0.05 wt %, about 0.1 wt%, about 0.5 wt %, about 1 wt %, about 2 wt %, about 3 wt %, about 5 wt%, or about 7 wt % to about 15 wt %, about 20 wt %, about 25 wt %, orabout 30 wt %, based on the dry weight of the lignocellulose substrates.In another example, the amount of the unsaturated compound in themixture can be about 0.1 wt %, about 0.5 wt %, about 1 wt %, about 3 wt%, or about 5 wt % to about 10 wt %, about 13 wt %, about 15 wt %, about17 wt %, or about 20 wt %, based on the dry weight of the lignocellulosesubstrates. In another example, the amount of the unsaturated compoundin the mixture can be about 1 wt % to about 15 wt %, about 5 wt % toabout 15 wt %, about 8 wt % to about 13 wt %, about 7 wt % to about 12wt %, or about 5 wt % to about 25 wt %, based on the dry weight of thelignocellulose substrates. In another example, the amount of theunsaturated compound in the mixture can be at least 0.5 wt %, at least 1wt %, at least 1.5 wt %, at least 2 wt %, at least 2.5 wt %, at least 3wt %, at least 3.5 wt %, at least 4 wt %, at least 4.5 wt %, at least 5wt %, at least 5.5 wt %, at least 6 wt %, at least 6.5 wt %, at least 7wt %, or at least 7.5 wt % to about 8 wt %, about 9 wt %, about 10 wt %,about 12 wt %, about 15 wt %, about 20 wt %, about 25 wt %, about 30 wt%, about 35 wt %, about 40 wt %, about 45 wt %, or about 50 wt %, basedon the dry weight of the lignocellulose substrates.

The amount of free radical precursor present in the mixture can depend,at least in part, on the particular composition of the free radicalprecursor, lignocellulose substrates, and/or the particular unsaturatedcompound and, thus, can widely vary. For example, the amount of radicalprecursor in the mixture can be about 0.05 wt %, about 0.1 wt %, about0.5 wt %, or about 1 wt % to about 50 wt %, about 100 wt %, about 150 wt%, or about 200 wt %, based on the dry weight of the lignocellulosesubstrates. In another example, the amount of radical precursor in themixture can be about 1 wt %, about 5 wt %, about 10 wt %, or about 20 wt% to about 80 wt %, about 100 wt %, about 120 wt %, or about 150 wt %,based on the dry weight of the lignocellulose substrates. In anotherexample, the radical precursor can be present in the mixture in anamount of about 0.1 wt % to about 30 wt %, about 1 wt % to about 20 wt%, about 5 wt % to about 50 wt %, about 10 wt % to about 70 wt %, about0.5 wt % to about 25 wt %, about 3 wt % to about 6 wt %, or about 2 wt %to about 8 wt %, based on the dry weight of the lignocellulosesubstrates. In still another example, the free radical precursor can bepresent in the mixture in amount of about 0.1 wt % to about 10 wt %,about 1 wt % to about 12 wt %, about 2 wt % to about 9 wt %, about 3 wt% to about 9 wt %, about 5 wt % to about 15 wt %, about 4 wt % to about6 wt %, about 8 wt % to about 20 wt %, or about 2 wt % to about 10 wt %,based on the dry weight of the lignocellulose substrates. In anotherexample, the amount of the free radical precursor can be present in themixture in an amount of at least 0.1 wt %, at least 0.3 wt %, at leastabout 0.5 wt %, at least about 0.7 wt %, at least about 1 wt %, at leastabout 1.3 wt %, at least about 1.5 wt %, at least about 1.7 wt %, atleast about 2 wt %, at least about 2.3 wt %, or at least about 2.5 wt %to about 5 wt %, about 7 wt %, about 10 wt %, about 15 wt %, about 20 wt%, about 25 wt %, about 30 wt %, about 35 wt %, about 40 wt %, about 45wt %, about 50 wt %, about 60 wt %, about 70 wt %, about 80 wt %, about90 wt %, about 100 wt %, about 120 wt %, about 140 wt %, or about 100 wt%, based on the dry weight of the lignocellulose substrates.

In at least one specific embodiment, the free radical precursor can beor include an inorganic oxidant, and the amount of inorganic oxidant inthe mixture can be about 0.05 wt %, about 0.1 wt %, about 0.5 wt %, orabout 1 wt % to about 50 wt %, about 100 wt %, about 150 wt %, or about200 wt %, based on the dry weight of the lignocellulose substrates. Inanother example, the inorganic oxidant can be present in the mixture inan amount of about 1 wt %, about 5 wt %, about 10 wt %, or about 20 wt %to about 80 wt %, about 100 wt %, about 120 wt %, or about 150 wt %,based on the dry weight of the lignocellulose substrates. In anotherexample, the inorganic oxidant can be present in the mixture in anamount of about 0.1 wt % to about 30 wt %, about 1 wt % to about 20 wt%, about 5 wt % to about 50 wt %, about 10 wt % to about 70 wt %, about0.5 wt % to about 25 wt %, about 3 wt % to about 6 wt %, or about 2 wt %to about 8 wt %, based on the dry weight of the lignocellulosesubstrates. In still another example, the inorganic oxidant can bepresent in the mixture in amount of about 0.1 wt % to about 10 wt %,about 1 wt % to about 12 wt %, about 2 wt % to about 9 wt %, about 3 wt% to about 9 wt %, about 5 wt % to about 15 wt %, about 4 wt % to about6 wt %, about 8 wt % to about 20 wt %, or about 2 wt % to about 10 wt %,based on the dry weight of the lignocellulose substrates. In yet anotherexample, the inorganic oxidant can be present in the mixture in anamount of at least 0.1 wt %, at least 0.3 wt %, at least about 0.5 wt %,at least about 0.7 wt %, at least about 1 wt %, at least about 1.3 wt %,at least about 1.5 wt %, at least about 1.7 wt %, at least about 2 wt %,at least about 2.3 wt %, or at least about 2.5 wt % to about 5 wt %,about 7 wt %, about 10 wt %, about 15 wt %, about 20 wt %, about 25 wt%, about 30 wt %, about 35 wt %, about 40 wt %, about 45 wt %, about 50wt %, about 60 wt %, about 70 wt %, about 80 wt %, about 90 wt %, about100 wt %, about 120 wt %, about 140 wt %, or about 100 wt %, based onthe dry weight of the lignocellulose substrates. In at least onespecific embodiment, the inorganic oxidant can be hydrogen peroxide.

The amount of catalyst or free radical precursor catalyst, if present inthe mixture, e.g., as a component of the free radical precursor, canwidely vary. For example, the amount of catalyst in the mixture can beabout 0.00001 wt %, about 0.0001 wt %, about 0.001 wt %, about 0.01 wt%, about 0.05 wt %, about 0.07 wt %, about 0.1 wt %, about 0.11 wt %,about 0.12 wt %, about 0.13 wt %, about 0.14 wt %, or about 0.15 wt % toabout 0.25 wt %, about 0.27 wt %, about 0.3 wt %, about 0.33 wt %, about0.35 wt %, bout 0.37 wt %, about 0.4 wt %, about 0.43 wt %, about 0.45wt %, about 0.47 wt %, about 0.5 wt %, about 0.6 wt %, about 0.7 wt %,about 0.8 wt %, about 0.9 wt %, about 1 wt %, about 2 wt %, about 3 wt%, about 4 wt %, about 5 wt %, or about 6 wt %, based on the dry weightof the lignocellulose substrates. In another example, the amount ofcatalyst in the mixture can be about 0.01 wt % to about 1.5 wt %, about0.1 wt % to about 1.3 wt %, about 0.05 wt % to about 0.5 wt %, or about0.07 wt % to about 0.4 wt %, based on the dry weight of thelignocellulose substrates. In another example, the amount of thecatalyst in the mixture can be about 0.001 wt % to about 0.5 wt %, about0.15 wt % to about 0.35 wt %, about 0.1 wt % to about 0.4 wt %, about0.1 wt % to about 2 wt %, about 0.05 wt % to about 3 wt %, or about 0.05wt % to about 0.35 wt %, based on the dry weight of the lignocellulosesubstrates.

The pH of the mixture can be acidic, neutral, or basic. For example, thepH of the mixture can be about 0.5, about 2, about 3, or about 4 toabout 7, about 7.5, about 8, about 8.5, or about 9. For example, themixture can have a pH of about 1.5 to about 9, about 2.5 to about 7,about 1 to about 5, about 5 to about 8, or about 3 to about 6. The pH ofthe mixture can be adjusted to any desired pH by combining one or morebase compounds and/or one or more acid compounds therewith. Suitablebase compounds and/or acid compounds can include those discussed anddescribed above and elsewhere herein.

One or more salts can optionally be combined with the lignocellulosesubstrates, the free radical precursor, the catalyst, the unsaturatedprepolymer, and/or the binder composition. The amount of salt in themixture, if present, can be about 1 wt %, about 2 wt %, or about 3 wt %to about 10 wt %, about 20 wt %, or about 30 wt %, based on the dryweight of the lignocellulose substrates. Illustrative metal cationsinclude, but are not limited to, Al, Ca, K, Na, Cu, Zn, Mg, Mn, Ba,and/or Li cations. Suitable anions can include, but are not limited to,carbonates, chlorides, nitrates, silicates, acetates, formates,sulphates, phosphates, and/or other forms. Illustrative salts caninclude, for example, calcium carbonate, and/or sodium nitrate.

If any one or more of the components discussed and described hereininclude two or more different compounds, those two or more differentcompounds can be present in any ratio with respect to one another. Saidanother way, if the mixture includes a first and a second type oflignocellulose substrate, catalyst, free radical precursor, and/orunsaturated prepolymer the amount of the first and second components canbe present in any desired ratio. For example, if the free radicalprecursor includes a first free radical precursor and a second freeradical precursor, the mixture can have a free radical precursorcomposition that includes the first free radical precursor in an amountof about 1 wt % to about 99 wt % and conversely about 99 wt % to about 1wt % of the second free radical precursor, based on the total weight ofthe first and second free radical precursors. In another example, theamount of the first free radical precursor can be about 5 wt %, about 10wt %, about 15 wt %, about 20 wt %, about 25 wt % about 30 wt %, about35 wt %, about 40 wt %, or about 45 wt % to about 60 wt %, about 65 wt%, about 70 wt %, about 75 wt %, about 80 wt %, about 85 wt %, about 90wt %, or about 95 wt %, based on the total weight of the first andsecond free radical precursors.

The mixture can be heated to produce the lignocellulose containingcomposite product or “composite product.” For example, the mixture canbe heated to a temperature of about 60° C., about 90° C., about 120° C.,about 150° C., or about 160° C. to about 170° C., about 200° C., about230° C., about 260° C., or about 300° C. to produce the compositeproduct. In another example, the mixture can be heated to a temperatureof at least 60° C., at least 70° C., at least 80° C., at least 90° C.,at least 100° C., at least 110° C., at least 120° C., at least 130° C.,or at least 140° C. to about 150° C., about 155° C., about 160° C.,about 165° C., about 170° C., about 180° C., about 200° C., about 225°C., about 250° C., about 275° C., or about 300° C. In another example,the mixture can be heated to a temperature of about 140° C. to about200° C., about 155° C. to about 175° C., about 160° C. to about 210° C.,about 160° C. to about 175° C., or about 145° C. to about 225° C.

In one or more embodiments, the mixture can be heated in air. In one ormore embodiments, the mixture can be heated in an atmosphere that isinert or non-reactive with the mixture or substantially an inertatmosphere. If the mixture is heated in a substantially inert atmospherethe amount of oxygen can be less than 5 mol %, less than 3 mol %, lessthan 1 mol %, le less than 0.5 mol %, less than 0.1 mol % oxygen.Suitable inert gases can include, but are not limited to, nitrogen,argon, or a mixture thereof.

Heating the mixture can cause or promote at least partial curing of themixture to produce the composite product. As used herein, the terms“curing,” “cured,” “at least partially curing,” “at least partiallycured,” and similar terms are intended to refer to the structural and/ormorphological change that occurs in the mixture, such as by covalentchemical reaction (crosslinking), ionic interaction or clustering, phasetransformation or inversion, and/or hydrogen bonding when the mixture issubjected to conditions sufficient, e.g., sufficiently heated, to causethe properties of a flexible, porous substrate, such as a nonwoven mator blanket of lignocellulose substrates and/or a rigid or semi-rigidsubstrate, such as a wood or other lignocellulose containing board orsheet, to which an effective amount of the binder composition has beenapplied, to be altered.

When the mixture is heated, the mixture can contain at least a portionof the free radical precursor initially added to and present in themixture. Said another way, at least a portion of the free radicalprecursor can remain unreacted or otherwise in the same form as whencombined with the additional components of the mixture. For example, ifthe free radical precursor includes one or more oxidants, e.g., hydrogenperoxide (H₂O₂), at least a portion of the oxidant in the form ofhydrogen peroxide can be present when heating of the mixture isinitiated or started. In one or more embodiments, the mixture cancontain at least 1%, at least 5%, at least 10%, at least 11%, at least13%, at least 15%, at least 20%, at least 25%, at least 30%, at least35%, at least 40%, at least 45%, at least 50%, at least 55%, at least60%, at least 65%, or at least 70% of the total amount of free radicalprecursor initially present in the mixture, e.g., the total amount ofthe free radical precursor combined with the plurality of lignocellulosesubstrates and the one or more unsaturated compounds having two or moreunsaturated carbon-carbon bonds, when the mixture is heated. In anotherexample, the mixture can contain about 1% to about 100%, about 11% toabout 95%, about 15% to about 85%, about 20% to about 90%, about 30% toabout 80%, about 11% to about 100%, about 35% to about 75%, about 40% toabout 70%, about 50% to about 70%, about 60% to about 80%, about 65% toabout 85%, or about 30% to about 95% of the total amount of free radicalprecursor initially present in the mixture when the mixture is heated.In at least one specific example, if the mixture can include about 5 wt% free radical precursor, based on the dry weight of the lignocellulosesubstrates when the mixture is initially formed and when the mixture isheated to a temperature of 60° C. or more at least 11% of the freeradical precursor can be present in the mixture. Said another way, ifthe mixture contains about 5 wt % of the one or more free radicalprecursors, based on the dry weight of the lignocellulose substrates,upon preparation or formation of the mixture, when heating the mixtureis initiated or started, the mixture can have a free radical precursorconcentration of at least 11% of the initial 5 wt % or 0.55 wt %, basedon the dry weight of the lignocellulose substrates.

In one or more embodiments, the amount of the one or more free radicalprecursors present when the mixture is heated, e.g., to a temperature ofabout 60° C. to about 300° C., can be at least 0.5 wt %, at least 0.7 wt%, at least 1 wt %, at least 1.2 wt %, at least 1.5 wt %, at least 1.7wt %, at least 2 wt %, at least 2.2 wt %, at least 2.5 wt %, at least2.7 wt %, at least 3 wt %, at least 3.2 wt %, at least 3.5 wt %, atleast 3.7 wt %, at least 4 wt %, at least 4.2 wt %, at least 4.5 wt %,at least 4.7 wt %, or at least 5 wt %, based on the dry weight of theplurality of lignocellulose substrates. For example, the amount of theone or more free radical precursors present when the mixture is heatedcan be about 1 wt %, about 1.5 wt %, about 1.6 wt %, about 1.8 wt %, orabout 2.1 wt % to high of about 5 wt %, about 7 wt %, about 10 wt %,about 15 wt %, about 20 wt % or more, based on the dry weight of theplurality of lignocellulose substrates. In another example, the amountof the one or more free radical precursors present when the mixture isheated can be about 1 wt % to about 10 wt %, about 1.5 wt % to about 7wt %, about 2 wt % to about 6 wt %, about 2.5 wt % to about 8 wt %,about 3 wt % to about 5.5 wt %, about 4 wt % to about 6.5 wt %, about2.2 wt % to about 11 wt %, or about 2.3 wt % to about 6.3 wt %, based onthe dry weight of the plurality of lignocellulose substrates.

The mixture can be heated as soon as the mixture is formed. The mixturecan be kept, held, or otherwise maintained at a temperature less than60° C. for a period of time prior to heating the mixture to atemperature of at least 60° C. At least one way an exothermic reactionbetween the components of the mixture can be substantially and/orsignificantly slowed and/or prevented such that the mixture does notsignificantly increase in temperature until the mixture is intentionallyheated can be to select an appropriate free radial precursor or mixtureof free radical precursors. In other words, the temperature of themixture, without external heat directed to the mixture, can remain freefrom or substantially free from the development of an exotherm byselectively selecting an appropriate free radical precursor(s). Theparticular temperature of the mixture during the time period beforeheating can depend, at least in part, on the ambient or environmentaltemperature where the mixture is located. In one or more embodiments,the mixture can be maintained at a temperature of less than 60° C.without any intentional removal of heat therefrom. In one or moreembodiments, the mixture can be maintained at a temperature of less than60° C. with removal of heat therefrom, e.g., the mixture can be locatedwithin a refrigeration device and/or a cooled fluid such as chilled aircan be directed toward and/or passed through the mixture. In one or moreembodiments, the mixture can be maintained at a temperature of less than60° C. by controlling or adjusting a water concentration of the mixture.For example, increasing the water concentration of the mixture canreduce, inhibit, or prevent the mixture from undergoing an exothermicreaction.

Prior to heating the mixture to a temperature of at least 60° C., themixture can be maintained at a temperature less than 60° C., less than55° C., less than 50° C., less than 45° C., less than 40° C., less than35° C., or less than 30° C. for at least 10 minutes, at least 13minutes, at least 15 minutes, at least 17 minutes, at least 20 minutes,at least 23 minutes, at least 25 minutes, at least 27 minutes, at least30 minutes, at least 33 minutes, at least 35 minutes, at least 37minutes, at least 40 minutes, at least 43 minutes, at least 45 minutes,at least 47 minutes, at least 50 minutes, at least 53 minutes, at least55 minutes, at least 57 minutes, or at least 60 minutes. For example,the mixture can be maintained at a temperature less than 60° C. for atleast 10 minutes to about 30 minutes, at least about 15 minutes to about35 minutes, at least about 20 minutes to about 40 minutes, at leastabout 18 minutes to about 45 minutes, or at least about 15 minutes toabout 40 minutes prior to heating the mixture to a temperature of atleast 60° C. In another example, the mixture can be maintained at atemperature less than 60° C. for at least 10 minutes, about 30 minutes,about 45 minutes, about 1 hour, about 2 hours, about 3 hours, about 5hours, about 12 hours, about 18 hours, about 24 hours, or about 30 hoursprior to heating the mixture to a temperature of at least 60° C.

Prior to heating the mixture to a temperature of at least 60° C., theamount of energy generated from the mixture due to exothermicreaction(s) between the components of the mixture can be less than 20cal/g of the mixture, less than 18 cal/g of the mixture, less than 16cal/g of the mixture, less than 15 cal/g of the mixture, less than 14cal/g of the mixture, or less than 13.8 cal/g of the mixture. Forexample, prior to heating the mixture to a temperature of at least 60°C., the amount of energy generated from the mixture due to exothermicreaction(s) between the components of the mixture can be less than 14cal/g, less than 13.5 cal/g, less than 13 cal/g, less than 12.5 cal/g,less than 12 cal/g, less than 11.5 cal/g, less than 11 cal/g, less than10.5 cal/g, less than 10 cal/g, less than 9.5 cal/g, less than 9 cal/g,less than 8.5 cal/g, less than 8 cal/g, less than 7.5 cal/g, less than 7cal/g, less than 6.5 cal/g, less than 6 cal/g, less than 5.5 cal/g, lessthan 5 cal/g, less than 4.5 cal/g, less than 4 cal/g, less than 3.5cal/g, less than 3 cal/g, less than 2.5 cal/g. less than 2 cal/g, lessthan 1.5 cal/g, less than 1 cal/g, or less than 0.5 cal/g of themixture.

Illustrative composite products discussed and described herein caninclude, but are not limited to, particleboard, fiberboard such asmedium density fiberboard (MDF) and/or high density fiberboard (HDF),plywood such as hardwood plywood and/or softwood plywood, orientedstrand board (OSB), laminated veneer lumber (LVL), laminated veneerboards (LVB), engineered wood flooring, and the like. Composite productsin the shape or form of a panel, sheet, board, or the like can be in theform of a rectangular prism that includes six outer surfaces, e.g.,three pairs of oppositely facing surfaces. The first pair of oppositelyfacing surfaces of the composite product can include a first or “top”surface and an opposing second or “bottom” surface. The second and thirdpairs of oppositely facing surfaces of the composite product can bereferred to as the “side surfaces” that have a surface area less thanthe surface area of the first and second surfaces. As such, compositeproducts in the shape or form of a panel, sheet, board, or the like canhave an average thickness, where the average thickness is the length ordistance between the first and second surfaces.

If the composite product is in the form of a panel, sheet, board, or thelike, the mixture can be heated for a time of about 5 seconds permillimeter (s/mm), about 10 s/mm, about 12 s/mm, or about 15 s/mm toabout 17 s/mm, about 19 s/mm, about 21 s/mm, about 23 s/mm, about 25s/mm, about 27 s/mm, about 30 s/mm, about 35 s/mm, about 40 s/mm, about50 s/mm, or about 60 s/mm, where the length refers to the averagethickness of the composite product. For example, the mixture can beheated for a time of about 7 s/mm to about 27 s/mm, about 9 s/mm toabout 24 s/mm, about 11 s/mm to about 22 s/mm, about 8 s/mm to about 20s/mm, about 14 s/mm to about 18 s/mm, about 6 s/mm to about 14 s/mm,about 10 s/mm to about 18 s/mm, or about 10 s/mm to about 16 s/mm, wherethe length refers to the average thickness of the composite product. Inanother example, the mixture can be heated for a time less than 22 s/mm,less than 20 s/mm, less than 18 s/mm, less than 17 s/mm, less than 16s/mm, less than 15 s/mm, less than 14 s/mm, less than 13 s/mm, or lessthan 12 s/mm, where the length refers to the average thickness of thecomposite product. In one specific example, a composite product in theform of a panel, sheet, board, or the like and having an averagethickness of about 15 mm and subjected to a total heating time of about4 minutes would correspond to heating the mixture for about 16 s/mm. Inat least one specific example, the mixture can be heated to atemperature of about 160° C. to about 170° C. for a time of 13 s/mm toabout 19 s/mm.

Pressure can optionally be applied to the mixture before, during, and/orafter the mixture is heated to produce the composite product. Forexample, if the desired composite product shape or structure is a panel,sheet, board, or the like, an amount of the mixture sufficient toproduce a composite product of the desired size, can be transported,directed, placed, introduced, disposed, or otherwise located within apress capable of pressing the mixture before the mixture is heatedand/or when the mixture is heated. The press can be an open press or aclosed press. In at least one specific embodiment, an open press can beused to press the mixture when the mixture is heated, e.g., to atemperature of about 100° C. to about 250° C. In another example, themixture can be extruded through a die (extrusion process) and heated toproduce the composite product. The mixture can be pressed under apressure of about 0.5 MPa, about 1 MPa, about 3 MPa, or about 5 MPa toabout 7 MPa, about 9 MPa, or about 11 MPa.

Illustrative open presses can be as discussed and described in U.S. Pat.Nos. 4,017,248; 5,337,655; 5,611,269; 5,950,532; 6,098,532; and6,782,810. Suitable, commercially available, open presses can include,but are not limited to, the CONTIROLL® press available from Siempelkampand the CPS press available from Dieffenbacher.

The composite product can have a density of about 0.5 g/cm³, about 0.55g/cm³, about 0.6 g/cm³, about 0.63 g/cm³, about 0.65 g/cm³, about 0.67g/cm³, or about 0.7 g/cm³ to about 0.75 g/cm³, about 0.77 g/cm³, about0.8 g/cm³, about 0.83 g/cm³, about 0.85 g/cm³, about 0.88 g/cm³, about0.9 g/cm³, about 0.93 g/cm³, about 0.95 g/cm³, about 0.97 g/cm³, about 1g/cm³, about 1.05 g/cm³, about 1.1 g/cm³, or about 1.2 g/cm³. Forexample, the composite product can have a density of about 0.5 g/cm³ toabout 1 g/cm³, about 0.7 g/cm³ to about 0.75 g/cm³, about 0.65 g/cm³ toabout 0.85 g/cm³, about 0.65 g/cm³ to about 0.8 g/cm³, about 0.67 g/cm³to about 0.77 g/cm³, or about 0.64 g/cm³ to about 0.8 g/cm³. In one ormore embodiments, the composite product can have density of less than0.88 g/cm³, less than 0.85 g/cm³, less than 0.83 g/cm³, less than 0.8g/cm³, less than 0.79 g/cm³, less than 0.78 g/cm³, less than 0.77 g/cm³,less than 0.76 g/cm³, less than 0.75 g/cm³, less than 0.74 g/cm³, orless than 0.73 g/cm³ and at least 0.5 g/cm³, at least 0.55 g/cm³, atleast 0.6 g/cm³, at least 0.65 g/cm³, or at least 0.7 g/cm³.

The composite product can have an internal bond strength of about 0.1MPa, about 0.2 MPa, about 0.3 MPa, about 0.35 MPa, about 0.4 MPa, about0.5 MPa, about 0.6 MPa, about 0.7 MPA, about 0.8 MPa, about 0.9 MPa,about 1 MPa, or about 1.1 MPa to about 1.5 MPa, about 2 MPa, about 2.5MPa, about 3 MPa, about 3.5 MPa, about 4 MPa, or about 5 MPa. Forexample, the composite product can have an internal bond strength ofabout 0.35 MPa to about 5.5 MPa, about 0.4 MPa to about 4.6 MPa, about0.48 MPa to about 3.8 MPa, about 0.6 MPa to about 3.2 MPa, about 0.8 MPato about 2.6 MPa, or about 0.5 MPa to about 2.1 MPa. In another example,the composite product can have an internal bond strength of about 0.5MPa to about 2 MPa, about 0.6 MPa to about 1.6 MPa, about 1 MPa to about1.7 MPa, about 0.6 MPa to about 1.2 MPa, or about 0.55 MPa to about 1.5MPa. In one or more embodiments, the composite product can have aninternal bond strength of at least 0.3 MPa, at least 0.33 MPa, at least0.35 MPa, at least 0.38 MPa, at least 0.41 MPa, at least 0.45 MPa, atleast 0.48 MPa, at least 0.51 MPa, at least 0.55 MPa, at least 0.58 MPa,at least 0.62 MPa, at least 0.65 MPa, at least 0.69 MPa, at least 0.72MPa, at least 0.76 MPa, or at least 0.79 MPa. The internal bond strengthfor each example can be determined according to the test procedureprovided for in ASTM D1037-06a.

In one or more embodiments, the composite product can have an internalbond strength of at least 0.4 MPa and can contain about 3 wt % of theunsaturated compound. In one or more embodiments, the composite productcan have an internal bond strength of at least 0.4 MPa and can containat least 3 wt % of the unsaturated compound. In one or more embodiments,the composite product can have an internal bond strength of at least 0.4MPa and can contain 3 wt % or less of the unsaturated compound. In oneor more embodiments, the composite product can have an internal bondstrength of about 0.5 MPa and can contain about 3.5 wt % of theunsaturated compound. In one or more embodiments, the composite productcan have an internal bond strength of at least 0.5 MPa and can containat least 3.5 wt % of the unsaturated compound. In one or moreembodiments, the composite product can have an internal bond strength ofat least 0.5 MPa and can contain 3.5 wt % or less of the unsaturatedcompound. In one or more embodiments, the composite product can have aninternal bond strength of at least 0.6 MPa and can contain about 4 wt %of the unsaturated compound. In one or more embodiments, the compositeproduct can have an internal bond strength of at least 0.6 MPa and cancontain at least 4 wt % of the unsaturated compound. In one or moreembodiments, the composite product can have an internal bond strength ofat least 0.6 MPa and can contain 4 wt % or less of the unsaturatedcompound. In one or more embodiments, the composite product can have aninternal bond strength of at least 0.8 MPa and can contain about 6 wt %of the unsaturated compound. In one or more embodiments, the compositeproduct can have an internal bond strength of at least 0.8 MPa and cancontain at least 6 wt % of the unsaturated compound. In one or moreembodiments, the composite product can have an internal bond strength ofat least 0.8 MPa and can contain 6 wt % or less of the unsaturatedcompound. In one or more embodiments, the composite product can have aninternal bond strength of at least 0.85 MPa and can contain about 6 wt %of the unsaturated compound. In one or more embodiments, the compositeproduct can have an internal bond strength of at least 0.85 MPa and cancontain at least 6 wt % of the unsaturated compound. In one or moreembodiments, the composite product can have an internal bond strength ofat least 0.85 MPa and can contain 6 wt % or less of the unsaturatedcompound. In one or more embodiments, the composite product can have aninternal bond strength of at least 1.1 MPa and can contain about 8 wt %of the unsaturated compound. In one or more embodiments, the compositeproduct can have an internal bond strength of at least 1.1 MPa and cancontain at least 8 wt % of the unsaturated compound. In one or moreembodiments, the composite product can have an internal bond strength ofat least 1.1 MPa and can contain 8 wt % or less of the unsaturatedcompound.

In one or more embodiments, the composite product can have a density ofless than 0.8 g/cm³, less than 0.79 g/cm³, less than 0.78 g/cm³, lessthan 0.77 g/cm³, less than 0.76 g/cm³, less than 0.75 g/cm³, less than0.74 g/cm³, or less than 0.73 g/cm³ and an internal bond strength of atleast 0.35 MPa, at least 0.4 MPa, at least 0.48 MPa, at least 0.51 MPa,at least 0.55 MPa, at least 0.58 MPa, at least 0.62 MPa, at least 0.65MPa, or at least 0.690 MPa. In at least one specific example, thecomposite product can have a density of less than 0.8 g/cm³ and aninternal bond strength of at least 0.48 MPa. In at least one otherspecific example, the composite product can have a density of less than0.8 g/cm³ and an internal bond strength of at least 0.69 MPa. In atleast one other specific example, the composite product can have adensity of less than 0.73 g/cm³ and an internal bond strength of atleast 0.48 MPa. In still another example, the composite product can havea density of less than 0.73 g/cm³ and an internal bond strength of atleast 0.58 MPa. In another example, the composite product can have adensity of less than 0.77 g/cm³ and an internal bond strength or atleast 0.58 MPa.

Composite products such as particleboard, fiberboard, plywood, andoriented strand board, can have a thickness or average thickness ofabout 1.5 mm, about 5 mm, or about 10 mm to about 30 mm, about 50 mm,about 100 mm, about 200 mm, or about 300 mm. Composite products such asparticleboard, fiberboard, plywood, and oriented strand board can have alength of about 0.1 m, about 0.5 m, about 1 m, about 1.2 m, about 1.8 m,about 2.4 m, about 3 m, or about 3.6 m. The composite products can alsohave a width of about 0.1 m, about 0.5 m, about 1 m, about 1.2 m, about1.8 m, about 2.4 m, or about 3 m.

The mixtures discussed and described herein can be free or essentiallyfree of formaldehyde for use in the production of the compositeproducts, e.g., wood products such as particleboard and plywood. As usedherein, the term “essentially free of formaldehyde” means the mixturedoes not include or contain any intentionally added formaldehyde orcompounds that can decompose, react, or otherwise form formaldehyde.Said another way, the term “essentially free of formaldehyde” means themixture does not contain formaldehyde or compounds that can formformaldehyde, but may include formaldehyde present as an impurity.Accordingly, depending on the particular multifunctional aldehyde(s)used to produce the mixtures discussed and described herein, the mixturecan be referred to as “no added formaldehyde” or “NAF” mixture.

The composite products discussed and described herein can exhibit a lowlevel of formaldehyde emission. A suitable test for determiningformaldehyde emission from a composite product can include ASTM D6007-02and AST E1333-10. For example, the composite products can exhibit aformaldehyde emission of zero. In another example, the compositeproducts can exhibit a formaldehyde emission of less than 1 part permillion (ppm), less than 0.9 ppm, less than 0.08 ppm, less than 0.07ppm, less than 0.06 ppm, less than 0.05 ppm, less than 0.04 ppm, lessthan 0.03 ppm, less than 0.02 ppm, less than 0.01 ppm, or less than0.005 ppm.

The composite product can meet or exceed the formaldehyde emissionstandards required by the California Air Resources Board (CARB) Phase 1(less than 0.1 parts per million “ppm” formaldehyde for particleboard),and Phase 2 (less than 0.09 ppm formaldehyde for particleboard). Thecomposite products discussed and described herein can also meet orexceed the formaldehyde emission standards required by the JapaneseJIS/JAS F*** (does not exceed 0.5 mg/L formaldehyde for particleboard),Japanese JIS/JAS F**** (does not exceed 0.3 mg/L formaldehyde forparticleboard), European E1, and European E2 standards.

EXAMPLES

In order to provide a better understanding of the foregoing discussion,the following non-limiting examples are offered. Although the examplesmay be directed to specific embodiments, they are not to be viewed aslimiting the invention in any specific respect. All parts, proportions,and percentages are by weight unless otherwise indicated.

Six unsaturated prepolymers (Prepolymers A-F) were prepared andparticleboard panels were made with the unsaturated prepolymers as partof the binder composition. More particularly, Prepolymers A-F were usedto make the particleboard panels of Examples 1-2, 3-4, 5-6, 7-9, 10-13,and 14-15, respectively. All prepolymers were used within 24 hours ofsynthesis.

Prepolymer A was synthesized from pentaerythritol and maleic anhydride.Maleic anhydride (205.8 g, 2.1 mol, purchased from across) andpentaerythritol (95.2 g, 0.7 mol, purchased from Acros) were added to a500 mL 3-neck round-bottom flask equipped with a mechanical stirrer, athermocouple, and a reflux condenser. The reactant mixture was heatedfrom room temperature to 60° C. and after 30 minutes the temperature wasincreased to 120° C. The reaction mixture was stirred at 120° C. for 1hour and the reactant mixture gradually turned into a light yellowsolution. The reaction mixture was cooled in air to less than 100° C.and water was added to make a 75 wt % solution. ¹³C NMR analysis of thepolymer (not diluted in water) showed that there is no freepentaerythritol left, monosubstituted pentaerythritol 1.4%,disubstituted pentaerythritol 13.3%, trisubstituted pentaerythritol44.4%, and tetrasubstituted pentaerythritol 41.1%.

Prepolymer B was synthesized from glycerol and itaconic acid. Itaconicacid (800 g, 6.15 moles, sample from Cargill), glycerol (800, 8.69moles, purchased from Aldrich), Fascat 4201 (1.6 g, from Archema Inc.),and hydroquinone (1.6 g from Aldrich) were added to a 1 L glass reactorequipped with a mechanical stirrer, a thermocouple, a moisture-trap witha three-way stopcock, and a cold-finger reflux condenser. The reactionwas conducted under a constant nitrogen purge. Over the course of 1hour, the reaction mixture was heated from room temperature to 182° C.when water began to be collected in the moisture trap. The reactionmixture was heated over the next hour up to 202° C. at which point 174.5g of condensate water had been collected. The glass reactor was placedin an ice bath and cooled to less than 100° C. After cooling to lessthan 100° C., 533 g of a 50% aqueous hydrogen peroxide solution(purchased from Degussa) was mixed with the cooled reaction product. Theproduct, Prepolymer B, was stored in a plastic container.

Prepolymer C was synthesized from glycerol and maleic anhydride. Maleicanhydride (645 g, 6.58 mol, purchased from Fisher), glycerol (855 g, 9.3mol, purchased from Aldrich), Fascat 4201 (1.5 g, purchased from ArchemaInc.), and Hydroquinone (1.5 g purchased from Aldrich) were added to a 1L glass reactor equipped with a mechanical stirrer, a thermocouple, amoisture-trap with a three-way stopcock, and a cold-finger refluxcondenser. Over the course of 20 minutes, the reaction mixture washeated from room temperature to 72° C., over which period the maleicanhydride melted. When the temperature of the reaction mixture reached72° C., the heating mantle was removed and the reaction was allowed toexotherm from 72° C. to 115° C. When the temperature reached 115° C.,the heating mantle was replaced and the reaction mixture was heated to158° C. when water began collecting in the moisture trap. The reactionmixture was heated to 206° C. at which point 98.1 g of condensate waterhad been collected. The glass reactor was placed in an ice bath andcooled to less than 100° C. After cooling to less than 100° C., 118 g ofwater was mixed with the cooled reaction product to lower the viscosityof the solution. The product, Prepolymer C, was stored in a plasticcontainer

Prepolymer D was synthesized from glycerol and maleic anhydride. Maleicanhydride (783 g, 8 mol, purchased from Fisher), glycerol (734 g, 8 mol,purchased from Aldrich), and Fascat 4201 (1.5 g, from Archema Inc.) wereadded to a 1 L glass reactor equipped with a mechanical stirrer, athermocouple, a moisture-trap with a three-way stopcock, and acold-finger reflux condenser. Over the course of 20 minutes the reactionmixture was heated from room temperature to 80° C., over which periodthe maleic anhydride melted. When the temperature of the reactionmixture reached 80° C., the heating mantle was removed and the reactionmixture was allowed to exotherm to 164° C. at which point water began todistill off from the reaction mixture. The loss of water cooled themixture to 155° C. The heating mantle was replaced, and the reactionmixture was maintained at 155° C., but no more water was collected. Thetotal amount of water collected was 5.4 g. The glass reactor was placedin an ice bath and cooled to less than 100° C. After cooling to lessthan 100° C., 360 g of the reaction mixture was combined with 120 g of50% aqueous hydrogen peroxide solution (purchased from Degussa).Prepolymer D was stored in a plastic container.

Prepolymer E was synthesized from polyglycerol and maleic anhydride.Polyglycerol (908 g, purchased from Cargill), was added to a 2 literresin kettle. The polyglycerol was heated to a temperature of 65° C. and518 g of powdered maleic anhydride (Aldrich Chemicals) was added. Thereaction mixture was allowed to exotherm to about 90° C. over 30minutes. A second charge of 420 g of maleic anhydride was added and thetemperature was allowed to exotherm to 105° C. over 30 minutes and washeld at 105° C. for an additional 90 minutes. The extent of the reactionwas monitored by infrared spectroscopy. When most of the maleicanhydride had reacted (disappearance of the anhydride bands in IRspectra) the reaction was cooled to about 70° C. followed by theaddition of 720 g of water. The mixture was then stirred until all thepolyester had dissolved to produce Prepolymer E. Prepolymer E as storedin a plastic container.

Prepolymer F was synthesized from polyglycerol, maltodextrin, and maleicanhydride: Polyglycerol (280 g, purchased from Cargill) and 200 g ofmaltodextrin (ADM) were added to a resin kettle. The temperature of themixture was raised to about 65° C. To the resulting white slurry wasadded 450 g of maleic anhydride in four portions over 3 hours. Duringthe course of these additions the temperature of the reaction wasgradually increased to 115° C. and held for an additional 30 minutes.The progress of the reaction was monitored by infrared spectroscopy.When most of the maleic anhydride had reacted (disappearance of theanhydride bands in IR spectra) the reaction mixture was cooled to about70° C. followed by the addition of 250 g of water. The reaction mixturewas stirred until all the polyester had dissolved. Prepolymer F wasstored in a plastic container.

For all examples (Ex. 1-15), 2,100 grams of face-grade wood particles(Southern Yellow Pine) was placed in 0.0283 m³ blender. The woodparticles had a moisture content of 5 wt % to 7 wt %. The components ofthe binder composition were then added to the wood particles in the formof a fine mist. The components were added in the following order: a) 4wt % to 8 wt % of the unsaturated polyester prepolymer (70-85% aq.), b)2 wt % to 4.5% hydrogen peroxide (50% aq.), and c) 0.17 wt % ironsulfate, with all amounts based on the dry weight of the wood particles.The resinated furnish had a moisture content of 13 wt % to 16 wt % andwas blended for 2 minutes after addition of the iron sulfate. Theresinated furnish was placed in a 40.64 cm×40.64 cm×5.08 cm form andpressed to stops configured to produce a panel having a thickness of1.58 cm+/−0.2 cm for 4 min at 165.5° C. (total press time of 240 secincluded a 30 sec closing time, a 180 sec press time at about 8,273.7and a 30 sec degas time). The particleboard samples were then cooled toroom temperature and internal bond (IB) strength was tested according toASTM D1037-06a.

TABLE 1 % Loading (Dry Weight of Wood Particles) Density IB ExamplePrepolymer Prepolymer H₂O₂ ³ FeSO₄ (g/cm³) (MPa) 1 A 4.5 2.0 0.1 0.820.82 2 A 8.0 2.0 0.1 0.85 1.33 3 B 4.0 2.0 0.1 0.80 0.72 4 B 8.0 2.0 0.10.79 0.99 5 C 5.5 2.0 0.1 0.82 0.77 6 C 8.0 2.0 0.1 0.82 0.88 7 D 4.54.5 0.1 0.82 0.38 8 D 5.5 2.0 0.1 0.81 0.43 9 D 8.0 2.0 0.1 0.81 0.61 10E 4.0 2.0 0.1 0.79 0.61 11 E 8.0 2.0 0.1 0.83 1.11 12 E¹ 4.0 2.0 0.10.82 0.71 13 E¹ 8.0 2.0 0.1 0.85 1.53 14 F 6.0 2.0 0.1 0.81 0.81 15 F²6.0 2.0 0.1 0.81 0.83 ¹Includes 20% TMPTA as an additive ²Includes 5%TMPTA as an additive ³Total loading of H₂O₂ (H₂O₂ used as a diluent istaken into account)

As shown in Table 1, particleboard panels having a density of 0.79 g/cm³to 0.85 g/cm³ and an internal bond strength from 0.38 MPa all the way upto 1.53 MPa were made.

Embodiments of the present disclosure further relate to any one or moreof the following paragraphs:

1. A binder composition, comprising: at least one unsaturated compoundhaving two or more unsaturated carbon-carbon bonds, wherein at least oneof the unsaturated carbon-carbon bonds is a pi-bond that is notconjugated with an aromatic moiety and is capable of free radicaladdition; and at least one free radical precursor, wherein the freeradical precursor is present in an amount of about 7 wt % to about 99 wt%, based on the weight of the one or more unsaturated compounds.

2. A binder composition, comprising: at least one unsaturated compoundhaving two or more unsaturated carbon-carbon bonds, wherein at least oneof the unsaturated carbon-carbon bonds is a pi-bond that is notconjugated with an aromatic moiety and is capable of free radicaladdition; at least one catalyst; and at least one oxidant, wherein theoxidant is present in an amount of about 7 wt % to about 99 wt %, basedon the weight of the one or more unsaturated compounds.

3. A binder composition, comprising: at least one unsaturated compoundhaving two or more unsaturated carbon-carbon bonds, wherein at least oneof the unsaturated carbon-carbon bonds is a pi-bond that is notconjugated with an aromatic moiety and is capable of free radicaladdition; and at least one free radical precursor comprising potassiumferricyanide, iron (S,S)-ethylenediamine-N,N′-disuccinic acid, ironethyleneglycol bis(2-aminoethylether)-N,N,N′,N′-tetraacetic acid, irontrans-1,2-diaminocyclohexanetetraacetic acid, nitrilotriacetic acid, orany mixture thereof.

4. A method for making a composite product, comprising: combining aplurality of lignocellulose substrates, at least one unsaturatedcompound, and at least one free radical precursor to produce a mixture,wherein the unsaturated compound has two or more unsaturatedcarbon-carbon bonds, and wherein at least one of the unsaturatedcarbon-carbon bonds is a pi-bond that is not conjugated with an aromaticmoiety and is capable of free radical addition; and heating the mixtureto a temperature of about 60° C. to about 300° C. to produce a compositeproduct.

5. A method for making a composite product, comprising: contacting aplurality of lignocellulose substrates with a binder compositioncomprising at least one unsaturated compound and at least one freeradical precursor to produce a mixture, wherein the unsaturated compoundhas two or more unsaturated carbon-carbon bonds, and wherein at leastone of the unsaturated carbon-carbon bonds is a pi-bond that is notconjugated with an aromatic moiety and is capable of free radicaladdition; and at least partially curing the binder composition toproduce a composite product.

6. A method for making a composite product, comprising: combining aplurality of lignocellulose substrates, at least one unsaturatedcompound, and at least one free radical precursor to produce a mixture,wherein the unsaturated compound has two or more unsaturatedcarbon-carbon bonds, wherein at least one of the unsaturatedcarbon-carbon bonds is a pi-bond that is not conjugated with an aromaticmoiety and is capable of free radical addition, and wherein the freeradical precursor is present in an amount of about 7 wt % to about 99 wt%, based on the weight of the one or more unsaturated compounds; andheating the mixture to a temperature of about 60° C. to about 300° C. toproduce a composite product.

7. A method for making a composite product, comprising: contacting aplurality of lignocellulose substrates with a binder compositioncomprising at least one unsaturated compound and at least one freeradical precursor to produce a mixture, wherein the unsaturated compoundhas two or more unsaturated carbon-carbon bonds, wherein at least one ofthe unsaturated carbon-carbon bonds is a pi-bond that is not conjugatedwith an aromatic moiety and is capable of free radical addition, andwherein the free radical precursor is present in an amount of about 7 wt% to about 99 wt %, based on the weight of the one or more unsaturatedcompounds; and at least partially curing the binder composition toproduce a composite product.

8. A method for making a composite product, comprising: combining aplurality of lignocellulose substrates, one or more unsaturatedcompounds, one or more oxidants, and one or more catalysts to produce amixture, wherein the one or more unsaturated compounds has two or moreunsaturated carbon-carbon bonds, wherein at least one of the unsaturatedcarbon-carbon bonds is a pi-bond that is not conjugated with an aromaticmoiety and is capable of free radical addition, and wherein the one ormore catalysts comprises a plurality of transition metal atoms eachbound to a corresponding complexing agent; and heating the mixture to atemperature of about 60° C. to about 300° C. to produce a compositeproduct, wherein at least 11 wt % of the one or more oxidants present inthe mixture is present when the mixture is heated to about 60° C. toabout 300° C.

9. A method for making a composite product, comprising: combining aplurality of lignocellulose substrates, one or more unsaturatedcompounds, one or more oxidants, and one or more catalysts to produce amixture, wherein the one or more unsaturated compounds has two or moreunsaturated carbon-carbon bonds, wherein at least one of the unsaturatedcarbon-carbon bonds is a pi-bond that is not conjugated with an aromaticmoiety and is capable of free radical addition, and wherein the one ormore catalysts comprises a plurality of transition metal atoms eachbound to a corresponding complexing agent; and heating the mixture to atemperature of about 60° C. to about 300° C. to produce a compositeproduct, wherein the one or more oxidants is present in an amount ofabout 11 wt %, based on the dry weight of the plurality oflignocellulose substrates when the mixture is heated to about 60° C. toabout 300° C.

10. A method for making a composite product, comprising: combining aplurality of lignocellulose substrates, at least one unsaturatedcompound, and at least one free radical precursor to produce a mixture,wherein the unsaturated compound has two or more unsaturatedcarbon-carbon bonds, wherein at least one of the unsaturatedcarbon-carbon bonds is a pi-bond that is not conjugated with an aromaticmoiety and is capable of free radical addition, and wherein the freeradical precursor comprises potassium ferricyanide, iron(S,S)-ethylenediamine-N,N′-disuccinic acid, iron ethyleneglycolbis(2-aminoethylether)-N,N,N′,N′-tetraacetic acid, irontrans-1,2-diaminocyclohexanetetraacetic acid, nitrilotriacetic acid, orany mixture thereof; and heating the mixture to a temperature of about60° C. to about 300° C. to produce a composite product.

11. A composite product, comprising a plurality of lignocellulosesubstrates and an at least partially cured binder composition, whereinthe binder composition, prior to at least partial curing, comprises atleast one unsaturated compound and at least one free radical precursor,wherein the unsaturated compound has two or more unsaturatedcarbon-carbon bonds, and wherein at least one of the unsaturatedcarbon-carbon bonds is a pi-bond that is not conjugated with an aromaticmoiety and is capable of free radical addition.

12. A composite product, comprising a plurality of lignocellulosesubstrates and an at least partially cured binder composition, whereinthe binder composition, prior to at least partial curing, comprises: atleast one unsaturated compound having two or more unsaturatedcarbon-carbon bonds, wherein at least one of the unsaturatedcarbon-carbon bonds is a pi-bond that is not conjugated with an aromaticmoiety and is capable of free radical addition; and at least one freeradical precursor, wherein the free radical precursor is present in anamount of about 7 wt % to about 99 wt %, based on the weight of the oneor more unsaturated compounds.

13. A composite product, comprising: an at least partially curedcomposition having a density of less than 1 g/cm³ and an internal bondstrength of at least 0.35 MPa, wherein the at least partiallycomposition, prior to curing, comprises a plurality of lignocellulosesubstrates, at least one unsaturated compound, and at least one freeradical precursor, wherein: the unsaturated compound has two or moreunsaturated carbon-carbon bonds, at least one of the unsaturatedcarbon-carbon bonds is a pi-bond that is not conjugated with an aromaticmoiety and is capable of free radical addition, and the free radicalprecursor is present in an amount of about 7 wt % to about 99 wt %,based on the weight of the one or more unsaturated compounds.

14. A composite product, comprising: an at least partially curedcomposition having a density of less than 1 g/cm³ and an internal bondstrength of at least 0.35 MPa, wherein the at least partiallycomposition, prior to curing, comprises a plurality of lignocellulosesubstrates, at least one unsaturated compound, and at least one freeradical precursor, wherein the unsaturated compound has two or moreunsaturated carbon-carbon bonds, and wherein at least one of theunsaturated carbon-carbon bonds is a pi-bond that is not conjugated withan aromatic moiety and is capable of free radical addition.

15. A composite product comprising a mixture that has been heated to atemperature of about 60° C. to about 300° C., wherein the mixture, priorto being heated, comprises a plurality of lignocellulose substrates, atleast one unsaturated compound, and at least one free radical precursor,wherein the unsaturated compound has two or more unsaturatedcarbon-carbon bonds, and wherein at least one of the unsaturatedcarbon-carbon bonds is a pi-bond that is not conjugated with an aromaticmoiety and is capable of free radical addition.

16. A composite product comprising a mixture that has been heated to atemperature of about 60° C. to about 300° C., wherein the mixture, priorto being heated, comprises a plurality of lignocellulose substrates, atleast one unsaturated compound, and at least one free radical precursor,wherein the unsaturated compound has two or more unsaturatedcarbon-carbon bonds, wherein at least one of the unsaturatedcarbon-carbon bonds is a pi-bond that is not conjugated with an aromaticmoiety and is capable of free radical addition, and wherein the heatedmixture has an internal bond strength of at least 0.35 MPa and a densityof less than 1 g/cm³.

17. A composite product having an internal bond strength of at least0.35 MPa and a density of less than 1 g/cm³, wherein the compositeproduct comprises a cured mixture of a plurality of lignocellulosesubstrates, at least one unsaturated compound, and at least one freeradical precursor, wherein the unsaturated compound has two or moreunsaturated carbon-carbon bonds, wherein at least one of the unsaturatedcarbon-carbon bonds is a pi-bond that is not conjugated with an aromaticmoiety and is capable of free radical addition.

18. A composite product comprising a cured mixture of a plurality oflignocellulose substrates, at least one unsaturated compound, and atleast one free radical precursor, wherein the unsaturated compound hastwo or more unsaturated carbon-carbon bonds, wherein at least one of theunsaturated carbon-carbon bonds is a pi-bond that is not conjugated withan aromatic moiety and is capable of free radical addition.

19. A composite product having an internal bond strength of at least0.35 MPa and a density of less than 1 g/cm³, wherein the compositeproduct comprises a mixture that has been heated to a temperature ofabout 60° C. to about 300° C., and wherein prior to heating the mixturecomprises a plurality of lignocellulose substrates, one or moreunsaturated compounds, and one or more free radical precursors, whereinthe one or more unsaturated compounds has two or more unsaturatedcarbon-carbon bonds, wherein at least one of the unsaturatedcarbon-carbon bonds is a pi-bond that is not conjugated with an aromaticmoiety and is capable of free radical addition.

20. A composite product comprising a plurality of lignocellulosesubstrates and an at least partially cured binder composition, whereinthe binder composition, prior to at least partial curing, comprises atleast one unsaturated compound, at least one catalyst, and at least oneoxidant, wherein the unsaturated compound has two or more unsaturatedcarbon-carbon bonds, and wherein at least one of the unsaturatedcarbon-carbon bonds is a pi-bond that is not conjugated with an aromaticmoiety and is capable of free radical addition.

21. A composite produce comprising a plurality of lignocellulosesubstrates and an at least partially cured binder composition, whereinthe binder composition, prior to at least partial curing, comprises atleast one unsaturated compound and at least one free radical precursor,wherein the unsaturated compound has two or more unsaturatedcarbon-carbon bonds, wherein at least one of the unsaturatedcarbon-carbon bonds is a pi-bond that is not conjugated with an aromaticmoiety and is capable of free radical addition, and wherein the freeradical precursor comprises potassium ferricyanide, iron(S,S)-ethylenediamine-N,N′-disuccinic acid, iron ethyleneglycolbis(2-aminoethylether)-N,N,N′,N′-tetraacetic acid, irontrans-1,2-diaminocyclohexanetetraacetic acid, nitrilotriacetic acid, orany mixture thereof.

22. The binder composition, method, or composite product according toany one of paragraphs 1, 3-7, and 10-19, and 21, wherein the freeradical precursor comprises a mixture of one or more inorganic oxidantsand one or more catalysts.

23. The binder composition, method, or composite product according toany one of paragraphs 1, 3-7, and 10-19, and 21, wherein the freeradical precursor comprises a mixture of hydrogen peroxide and one ormore iron containing catalysts.

24. The binder composition, method, or composite product according toany one of paragraphs 1, 3-7, and 10-19, and 21, wherein the freeradical precursor is present in an amount of at least 30 wt % to about99 wt %, based on the weight of the one or more unsaturated compounds.

25. The binder composition, method, or composite product according toany one of paragraphs 1, 3-7, and 10-19, and 21, wherein the freeradical precursor comprises a mixture of hydrogen peroxide and one ormore catalysts, wherein the hydrogen peroxide is present in an amount ofabout 10 wt % to about 80 wt %, based on the combined weight of theunsaturated compound and the free radical precursor, and wherein the oneor more catalysts is present in an amount of about 0.01 wt % to about 20wt %, based on the combined weight of the unsaturated compound and thefree radical precursor.

26. The binder composition, method, or composite product according toany one of paragraphs 1, 3-7, and 10-19, and 21, wherein the freeradical precursor comprises one or more catalysts, wherein the one ormore catalysts comprises one or more transition metal atoms, and whereinthe one or more transition metal atoms is each bound to a correspondingcomplexing agent.

27. The binder composition, method, or composite product according toparagraph 26, wherein the one or more transition metal atoms is iron,copper, manganese, tungsten, molybdenum, cobalt, titanium, or anymixture thereof.

28. The binder composition, method, or composite product according toany one of paragraphs 1, 3-7, and 10-19, and 21, wherein the freeradical precursor comprises one or more catalysts, wherein the one ormore catalysts comprises one or more metal ions of iron, copper,manganese, tungsten, molybdenum, or any mixture thereof; or acombination thereof.

29. The binder composition, method, or composite product according toany one of paragraphs 1, 3-7, and 10-19, and 21, wherein the freeradical precursor comprises one or more catalysts, and wherein the oneor more catalysts comprises one or more transition metals withcoordinated Lewis bases.

30. The binder composition, method, or composite product according toany one of paragraphs 1, 3-7, and 10-19, and 21, wherein the freeradical precursor comprises one or more catalysts, and wherein the oneor more catalysts is potassium ferricyanide, ironethylenediaminetetraacetic acid, iron(S,S)-ethylenediamine-N,N′-disuccinic acid, iron diethylenetriaminepentaacetic acid, iron ethyleneglycolbis(2-aminoethylether)-N,N,N′,N′-tetraacetic acid, irontrans-1,2-diaminocyclohexanetetraacetic acid, or any mixture thereof.

31. The binder composition, method, or composite product according toany one of paragraphs 1, 3-7, and 10-19, and 21, wherein the one or morefree-radical precursors comprises one or more inorganic peroxycompounds, one or more organic peroxy compounds, or a mixture thereof.

32. The binder composition, method, or composite product according toany one of paragraphs 25-30, wherein the one or more catalysts ispresent in an amount of about 0.02 wt % to about 15 wt %, based on thecombined weight of the unsaturated compound and the free-radicalprecursor.

33. The binder composition, method, or composite product according toany one of paragraphs 1, 3-7, and 10-19, and 21, wherein the one or morefree-radical precursors is present in an amount of about 1 wt % to about50 wt %, based on the combined weight of the unsaturated compound andthe free-radical precursor.

34. The binder composition, method, or composite product according toany one of paragraphs 1, 3-7, and 10-19, and 21, wherein the freeradical precursor comprise azobisisobutyronitrile.

35. The binder composition, method, or composite product according toany one of paragraphs 1 to 34, wherein the carbon-carbon bond capable offree radical addition is an α,β-unsaturated carbonyl.

36. The binder composition, method, or composite product according toany one of paragraphs 1 to 35, wherein the unsaturated compoundcomprises dicyclopentadiene, ethylene glycol diacrylate, ethylene glycoldimethacrylate, diethylene glycol diacrylate, diethylene glycoldimethacrylate, poly(ethylene glycol) diacrylate, poly(ethylene glycol)dimethacrylate, trimethylolpropane triacrylate, pentaerythritoltetraacrylate, pentaerythritol triacrylate, polyacrylate starch, linseedoil, an unsaturated prepolymer, or any mixture thereof.

37. The binder composition, method, or composite product according toparagraph 36, wherein the unsaturated prepolymer is present andcomprises an unsaturated polyester prepolymer, an unsaturated polyetherprepolymer; an unsaturated polyamide prepolymer, an unsaturatedpolyurethane prepolymer, or any mixture thereof.

38. The binder composition, method, or composite product according toparagraph 37, wherein the unsaturated polyester prepolymer is present.

39. The binder composition, method, or composite product according toparagraph 37, wherein the unsaturated polyether prepolymer is present.

40. The binder composition, method, or composite product according toparagraph 37, wherein the unsaturated polyamide prepolymer is present.

41. The binder composition, method, or composite product according toparagraph 37, wherein the one or more unsaturated polyurethaneprepolymers is present.

42. The binder composition, method, or composite product according toparagraph 37, wherein the unsaturated prepolymer is water soluble, waterdispersible, or water emulsifiable.

43. The binder composition, method, or composite product according toparagraph 37, wherein the unsaturated prepolymer has a double bondequivalent molecular weight of about 33 to about 250,000.

44. The binder composition, method, or composite product according toany one of paragraphs 1-3, 5, 7, 11, 12, 20, and 21, wherein the bindercomposition has a viscosity of about 20 cP to about 300,000 cP at atemperature of 25° C.

45. The binder composition, method, or composite product according toany one of paragraphs 1-3, 5, 7, 11, 12, 20, and 21, wherein the bindercomposition has a pH of about 0.5 to about 8.5.

46. The binder composition, method, or composite product according toany one of paragraphs 1, 3-6, and 9-18, wherein the unsaturated compoundis present in an amount of about 50 wt % to about 99 wt %, based on thecombined weight of the unsaturated compound and the free-radicalprecursor.

47. The binder composition, method, or composite product according toany one of paragraphs 2, 8, 9, and 20, wherein the unsaturated compoundis present in an amount of about 50 wt % to about 99 wt %, based on thecombined weight of the unsaturated compound, catalyst, and the oxidant.

48. The binder composition, method, or composite product according toany one of paragraphs 1 to 47, wherein the unsaturated prepolymer has aviscosity of about 20 cP to about 50,000 cP at a temperature of 25° C.

49. The method according to any one of paragraphs 4, 6, and 8-10,further comprising pressing the mixture to a pressure greater thanatmospheric pressure when the mixture is heated.

50. The method according to any one of paragraphs 4, 6, and 8-10,further comprising pressing the mixture to a pressure of about 0.1 MPato about 10 MPa when the mixture is heated.

51. The method or composite product according to any one of paragraphs 4to 50, wherein the composite product has an internal bond strength of atleast 0.35 MPa to about 5 MPa.

52. The method or composite product according to any one of paragraphs 4to 50, wherein the composite product has a density of about 0.5 g/cm³ toabout 1.0 g/cm³.

53. The method or composite product according to any one of paragraphs 4to 50, wherein the composite product has an internal bond strength of atleast 0.35 MPa to about 5 MPa and a density of about 0.5 g/cm³ to about1.0 g/cm³.

54. The method or composite product according to any one of paragraphs 4to 53, wherein the composite product comprises a particleboard, afiberboard, a plywood, an oriented strand board, a laminated veneerlumber, parallel strand lumber, or a laminated veneer board.

55. The binder composition, method, or composite product according toany one of paragraphs 1-7, 9-19, or 21-54, wherein the free radicalprecursor is present in an amount of about 7 wt %, about 10 wt %, about12 wt %, about 15 wt %, about 20 wt %, about 25 wt %, about 30 wt %,about 35 wt %, about 40 wt %, bout 45 wt %, or about 50 wt % to about 75wt %, about 80 wt %, about 85 wt %, about 90 wt %, about 95 wt %, orabout 99 wt %, based on the combined weight of the one or moreunsaturated compounds and the free radical precursor.

56. The binder composition, method, or composite product according toany one of paragraphs 1-7, 9-19, or 21-54, wherein the free radicalprecursor is present in an amount of about 7 wt %, about 10 wt %, about12 wt %, about 15 wt %, about 20 wt %, about 25 wt %, about 30 wt %,about 35 wt %, about 40 wt %, bout 45 wt %, or about 50 wt % to about 75wt %, about 80 wt %, about 85 wt %, about 90 wt %, about 95 wt %, orabout 99 wt %, based on the weight of the one or more unsaturatedcompounds.

57. The binder composition, method, or composite product according toany one of paragraphs 1 to 56, wherein the unsaturated compoundcomprises the unsaturated prepolymer, and wherein the unsaturatedprepolymer comprises a reaction product of maleic acid and a polyol, areaction product of fumaric acid and a polyol, or a mixture thereof.

58. A binder composition, comprising: at least one unsaturated compoundhaving two or more unsaturated carbon-carbon bonds, wherein at least oneof the unsaturated carbon-carbon bonds is a pi-bond that is notconjugated with an aromatic moiety and is capable of free radicaladdition; and at least one free radical precursor, wherein the freeradical precursor is present in an amount of about 7 wt % to about 99 wt%, based on the combined weight of the unsaturated compounds and thefree radical precursor.

59. A binder composition, comprising: at least one unsaturated compoundand at least one free radical precursor, wherein the free radicalprecursor is present in an amount of about 7 wt % to about 99 wt %,based on the weight of the unsaturated compound, and wherein theunsaturated compound comprises one or more vinyl aromatics, one or moremethylstyrenes, or any mixture thereof.

60. A binder composition, comprising: at least one unsaturated compoundand at least one free radical precursor, wherein the free radicalprecursor is present in an amount of about 7 wt % to about 99 wt %,based on the combined weight of the unsaturated compound and the freeradical precursor, and wherein the unsaturated compound comprises one ormore vinyl aromatics, one or more methylstyrenes, or any mixturethereof.

61. The binder composition according to any one of paragraphs 58 to 60,wherein the free radical precursor comprises a mixture of one or moreinorganic oxidants and one or more catalysts.

62. The binder composition according to any one of paragraphs 58 to 60,wherein the free radical precursor comprises a mixture of hydrogenperoxide and one or more iron containing catalysts.

63. The binder composition according to any one of paragraphs 58 to 62,wherein the free radical precursor is present in an amount of at least30 wt % to about 99 wt %, based on the weight of the one or moreunsaturated compounds.

64. The binder composition according to any one of paragraphs 58 to 60,wherein the free radical precursor comprises a mixture of hydrogenperoxide and one or more catalysts, wherein the hydrogen peroxide ispresent in an amount of about 10 wt % to about 80 wt %, based on thecombined weight of the unsaturated compound and the free radicalprecursor, and wherein the one or more catalysts is present in an amountof about 0.01 wt % to about 20 wt %, based on the combined weight of theunsaturated compound and the free radical precursor.

65. The binder composition according to any one of paragraphs 58 to 60,wherein the free radical precursor comprises one or more catalysts,wherein the one or more catalysts comprises one or more transition metalatoms, and wherein the one or more transition metal atoms is each boundto a corresponding complexing agent.

66. The binder composition according to paragraphs 65, wherein the oneor more transition metal atoms is iron, copper, manganese, tungsten,molybdenum, cobalt, titanium, or any mixture thereof.

67. The binder composition according to any one of paragraphs 58 to 60,wherein the free radical precursor comprises one or more catalysts,wherein the one or more catalysts comprises one or more metal ions ofiron, copper, manganese, tungsten, molybdenum, or any mixture thereof;or a combination thereof.

68. The binder composition according to any one of paragraphs 58 to 60,wherein the free radical precursor comprises one or more catalysts, andwherein the one or more catalysts comprises one or more transitionmetals with coordinated Lewis bases.

69. The binder composition according to any one of paragraphs 58 to 60,wherein the free radical precursor comprises one or more catalysts, andwherein the one or more catalysts is potassium ferricyanide, ironethylenediaminetetraacetic acid, iron(S,S)-ethylenediamine-N,N′-disuccinic acid, iron diethylenetriaminepentaacetic acid, iron ethyleneglycolbis(2-aminoethylether)-N,N,N′,N′-tetraacetic acid, irontrans-1,2-diaminocyclohexanetetraacetic acid, or any mixture thereof.

70. The binder composition according to any one of paragraphs 58 to 60,wherein the free radical precursor comprise azobisisobutyronitrile.

71. The binder composition according to any one of paragraphs 58 to 60,wherein the carbon-carbon bond capable of free radical addition is anα,β-unsaturated carbonyl.

72. The binder composition according to any one of paragraphs 58 to 71,wherein the unsaturated compound comprises dicyclopentadiene, ethyleneglycol diacrylate, ethylene glycol dimethacrylate, diethylene glycoldiacrylate, diethylene glycol dimethacrylate, poly(ethylene glycol)diacrylate, poly(ethylene glycol) dimethacrylate, trimethylolpropanetriacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate,polyacrylate starch, linseed oil, an unsaturated prepolymer, or anymixture thereof.

73. The binder composition according to paragraphs 72, wherein theunsaturated prepolymer is present and comprises an unsaturated polyesterprepolymer, an unsaturated polyether prepolymer; an unsaturatedpolyamide prepolymer, an unsaturated polyurethane prepolymer, or anymixture thereof.

74. The binder composition according to any one of paragraphs 58 to 60,wherein the unsaturated compound is present in an amount of about 50 wt% to about 99 wt %, based on the combined weight of the unsaturatedcompound and the free-radical precursor.

75. The binder composition according to any one of paragraphs 58 to 60,wherein the free radical precursor is present in an amount of about 7 wt%, about 10 wt %, about 12 wt %, about 15 wt %, about 20 wt %, about 25wt %, about 30 wt %, about 35 wt %, about 40 wt %, bout 45 wt %, orabout 50 wt % to about 75 wt %, about 80 wt %, about 85 wt %, about 90wt %, about 95 wt %, or about 99 wt %, based on the combined weight ofthe one or more unsaturated compounds and the free radical precursor.

76. The binder composition according to any one of paragraphs 58 to 60,wherein the free radical precursor is present in an amount of about 7 wt%, about 10 wt %, about 12 wt %, about 15 wt %, about 20 wt %, about 25wt %, about 30 wt %, about 35 wt %, about 40 wt %, bout 45 wt %, orabout 50 wt % to about 75 wt %, about 80 wt %, about 85 wt %, about 90wt %, about 95 wt %, or about 99 wt %, based on the weight of the one ormore unsaturated compounds.

77. The binder composition according to any one of paragraphs 58 to 60,wherein the unsaturated compound comprises an unsaturated prepolymer,and wherein the unsaturated prepolymer comprises a reaction product ofmaleic acid and a polyol, a reaction product of fumaric acid and apolyol, or a mixture thereof.

Certain embodiments and features have been described using a set ofnumerical upper limits and a set of numerical lower limits. It should beappreciated that ranges including the combination of any two values,e.g., the combination of any lower value with any upper value, thecombination of any two lower values, and/or the combination of any twoupper values are contemplated unless otherwise indicated. Certain lowerlimits, upper limits and ranges appear in one or more claims below. Allnumerical values are “about” or “approximately” the indicated value, andtake into account experimental error and variations that would beexpected by a person having ordinary skill in the art.

Various terms have been defined above. To the extent a term used in aclaim is not defined above, it should be given the broadest definitionpersons in the pertinent art have given that term as reflected in atleast one printed publication or issued patent. Furthermore, allpatents, test procedures, and other documents cited in this applicationare fully incorporated by reference to the extent such disclosure is notinconsistent with this application and for all jurisdictions in whichsuch incorporation is permitted.

While the foregoing is directed to embodiments of the present invention,other and further embodiments of the invention may be devised withoutdeparting from the basic scope thereof, and the scope thereof isdetermined by the claims that follow.

What is claimed is:
 1. A binder composition, comprising: an unsaturatedcompound comprising a reaction product of (1) a prepolymer and (2) anunsaturated alcohol, an unsaturated acid, an unsaturated epoxide, or amixture thereof, wherein the prepolymer comprises an unsaturatedpolyester prepolymer, an unsaturated polyamide prepolymer, anunsaturated polyether prepolymer, an unsaturated polyurethaneprepolymer, or a mixture thereof; and a free radical precursorcomprising an oxidant and a catalyst.
 2. The binder composition of claim1, wherein the oxidant comprises an inorganic oxidant.
 3. The bindercomposition of claim 1, wherein a weight ratio of the free radicalprecursor to the unsaturated compound is at least 0.23:1 to about 40:1.4. The binder composition of claim 3, wherein the oxidant compriseshydrogen peroxide and the catalyst comprises an iron containingcatalyst.
 5. The binder composition of claim 1, wherein the unsaturatedcompound comprises a reaction product of (1) the prepolymer and (2) theunsaturated alcohol.
 6. The binder composition of claim 5, wherein theunsaturated alcohol comprises an allylic alcohol.
 7. The bindercomposition of claim 1, wherein the unsaturated compound comprises areaction product of (1) the prepolymer and (2) the unsaturated acid. 8.The binder composition of claim 7, wherein the unsaturated acidcomprises an unsaturated polyacid.
 9. The binder composition of claim 1,wherein the unsaturated compound comprises a reaction product of (1) theprepolymer and (2) the unsaturated epoxide.
 10. The binder compositionof claim 9, wherein the unsaturated epoxide comprises allyl glycidylether; 3,4-epoxy-1-butene; 1,2-epoxy-5-hexene; or a mixture thereof. 11.The binder composition of claim 1, wherein: the unsaturated compoundcomprises a reaction product of (1) the prepolymer and (2) theunsaturated epoxide, the prepolymer comprises the unsaturated polyesterprepolymer, and the unsaturated epoxide comprises allyl glycidyl ether.12. A binder composition, comprising: a first unsaturated compoundcomprising a prepolymer selected from the group consisting of: anunsaturated polyester prepolymer, an unsaturated polyamide prepolymer,an unsaturated polyether prepolymer, an unsaturated polyurethaneprepolymer, and a mixture thereof; a second unsaturated compoundselected from the group consisting of: dicyclopentadiene, ethyleneglycol diacrylate, ethylene glycol dimethacrylate, diethylene glycoldiacrylate, diethylene glycol dimethacrylate, poly(ethylene glycol)diacrylate, poly(ethylene glycol) dimethacrylate, trimethylolpropanetriacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate,polyacrylate starch, and a mixture thereof; and a free radical precursorcomprising an oxidant and a catalyst.
 13. The binder composition ofclaim 12, wherein a weight ratio of the free radical precursor to acombined weight of the first unsaturated compound and the secondunsaturated compound is at least 0.23:1 to about 40:1.
 14. The bindercomposition of claim 13, wherein the oxidant comprises hydrogenperoxide, and wherein the catalyst comprises an iron-containingcatalyst.
 15. A binder composition, comprising: a first unsaturatedcompound comprising a reaction product of (1) a prepolymer and (2) anunsaturated alcohol, an unsaturated acid, an unsaturated epoxide, or amixture thereof, wherein the prepolymer comprises an unsaturatedpolyester prepolymer, an unsaturated polyamide prepolymer, anunsaturated polyether prepolymer, an unsaturated polyurethaneprepolymer, or a mixture thereof; a second unsaturated compound selectedfrom the group consisting of: dicyclopentadiene, ethylene glycoldiacrylate, ethylene glycol dimethacrylate, diethylene glycoldiacrylate, diethylene glycol dimethacrylate, poly(ethylene glycol)diacrylate, poly(ethylene glycol) dimethacrylate, trimethylolpropanetriacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate,polyacrylate starch, and a mixture thereof; and a free radical precursorcomprising an oxidant and a catalyst.
 16. The binder composition ofclaim 15, wherein a weight ratio of the free radical precursor to acombined weight of the first unsaturated compound and the secondunsaturated compound is at least 0.23:1 to about 40:1.
 17. The bindercomposition of claim 16, wherein the oxidant comprises hydrogenperoxide, and wherein the catalyst comprises an iron-containingcatalyst.
 18. The binder composition of claim 15, wherein theunsaturated compound comprises a reaction product of (1) the prepolymerand (2) the unsaturated alcohol.
 19. The binder composition of claim 15,wherein the unsaturated compound comprises a reaction product of (1) theprepolymer and (2) the unsaturated acid.
 20. The binder composition ofclaim 15, wherein the unsaturated compound comprises a reaction productof (1) the prepolymer and (2) the unsaturated epoxide.